There's a lot of good info here, but also some stuff in this thread that could lead to confusion, so I'd like to chip in my tuppence worth to hopefully clarify some of it.
First some facts on gases and liquids. Both are fluids, but gases are generally treated as compressible and liquids not and pretty much everything I can think of resists compression (or they'd collapse into nothing under atmospheric pressure). However, air is much, much more compressible than water. If I recall correctly, I think the figure is about 20,000 times more compressible. It is therefore a fair assumption that in a system containing air and water, any compression of water is negligible compared to that of air.
However, as indicated by the Great Pretender, the density of the liquid is different to it's compressibility. 13 litres of 50% water/50 % propylene glycol mix put into the system at a temp of 30 deg C will only be 12.75 litres at -10 deg C. The compressibility of the air makes up for these differences, resulting in a change of pressure inside a closed cooling system.
The bongo cooling system contains about 13 litres of liquid, and at an estimate, about 2 litres of air in the expansion tank.
The radiator cap opens when the pressure inside the coolant system is 1.1 bar greater than the pressure outside, i.e. atmospheric pressure. So if you fill your system on a very high pressure day (say atmos pressure of 1.04 bar), put the cap on and, without having driven, open the cap on a day when the temp is about the same, but the atmos pressure is very low (say 0.97 bar), then your system will vent pressure when you open it because the system has 0.07 bar more pressure than the atmosphere. If you do it the other way around it'll take in pressure when you open the cap. Similarly, if you open the cap when the temperature is higher than when you filled it there will be positive pressure, and negative pressure if the temperature is cooler.
Of course we all drive our Bongos resulting in temp changes in the coolant. Say we filled the system with 13 litres on a day when the temp was 20 deg C. Assume atmospheric pressure to be a constant 1 bar and that the cooling system has a constant capacity of 15 litres (i.e. no expansion of pipes and 2 litres of air in the expansion tank after filling). Pressure x Volume / temp (in Kelvin) is constant for an ideal gas, and air is close enough to an ideal gas. Then as the engine temp heated up the following would happen in a sealed system.
(These figure correlate well with the 10-13psi that Matt quotes for a healthy system, corresponding to a running temp range of about 88 deg C +/- 5deg, so I guess that the 2L of air estimate is quite accurate.)
When the pressure reaches 2.1bar (i.e. 1.1 bar above atmospheric pressure) the vent cap opens and excess air is slowly expelled as the engine heats up maintaining a pressure differential of 1.1 bar. When the coolant temp starts dropping this vent cap closes and the system is again sealed. As the coolant cools to ambient temperature the pressure in the system drops.
The temperature and amount of coolant you use when filling dictates this curve. The more coolant you put in, the more extreme the effect, as the volume changes by more with temperature. I calculate that the vent cap will open at 15 degrees lower temp if you overfill by only 0.5 a litre (i.e. 13.5 L coolant, 1.5 L air). Of course the difference in atmospheric pressure between the time the vent closes and when you next open the expansion tank cap could also result in the effects described a couple of paragraphs back.
It's often said on here to fill right up to the max line. I don't believe that this is a good general rule. The max and min lines are to allow some user error and to allow expansion and contraction of the coolant with ambient temperature. If you do have a leak, overfilling won't buy you significantly more time, as you will be pressurising that weak spot more than had you filled to the min line, potentially accelerating the failure.
Any contraction of pipes etc during cooling will result in a positive pressure, possibly keeping the pipes partially swollen.
So there are many reasons for both an intake or expulsion of air when removing the expansion tank cap. There is a limit to the upper pressure (1.1 bar more than atmosphere), and from the info on this thread it appears there is also a negative pressure limit (I'll have to check my expansion tank cap because I thought there was just the one spring on mine). The upper limit should only be reached when the engine is working very hard, and a lower limit of -1psi only reached during significant changes in environmental conditions from the last time the vent opened.
However, in any situation, the coolant level should not change by solely by opening the expansion tank cap on a cold system. If it does it means that something else is changing volume, not the coolant.
One reason could be very dodgy rubber pipes - they could have expanded when pressurised and, when the cap is removed, contracted. Any change in their volume will directly correlate with the expansion tank level.
Another reason could be air trapped somewhere in the cooling loop. In this case the change in level will be proportional to the ratio of trapped air to the volume of air in the tank. The system needs urgently bled if this is the case.
Exhaust gases could cause the pressurisation while running, but should be vented. What they could easily do though is add a compressible gas trapped inside the coolant loop as above.
So basically follow Simon Jones' advice and if that doesn't show anything you may have a problem similar to Matt (Driver and Passengers).
(Regarding some of the other stuff mentioned here:
1) Water boils and forms gases at a relatively low temperature. Gases are very compressible - not good under hard braking just when temps rise. I like my brakes to work below zero degrees C, when water becomes solid. Other liquids, as well as being more suitable for these reasons, are also more easily sealed. These are more important reasons why water is not used as a brake fluid.
2) If water were suddenly to become far more compressible, then ships would experience problems. However, we could still design them such that they would float. Helium balloons float in air. Air is compressible. )