On the typical "open" system, the radiator cap actually has two valves in it...
One is the "pressure relief valve" (PRV) that works to keep the cooling system at or near specified pressure. When you see the "pounds" rating on the cap (typically 6/13/15/16,) that's the pressure that the cap is rated to hold, in psig (pounds per square inch, gage - or, pounds above atmospheric pressure.)
The other is the "vacuum relief valve" (VRV) - which is what allows overflow coolant to be drawn back into the system. You'll probably note that the overflow hose is connected at the bottom of the overflow tank - there's a reason for this.
As most things (like coolant) are heated, they tend to expand. The point of the overflow tank is to chatch this expanded coolant for re-use. Coolant in the overflow tank, above and beyond the small amount that is specified to go in there for a system fill, is coolant that expanded past the PRV, and therefore went down the overflow hose into the overflow catch tank.
When the system cools down, the coolant again contracts, which creates an air space above the coolant in the radiator. Since no air is allowed in there, you have a relative vacuum between the radiator and the ambient air pressure - this is where the VRV comes in.
Once a vacuum is set up in the radiator, the VRV opens, and coolant is passed through the VRV back into the radiator, impelled by atmospheric pressure (to be technical, it isn't "sucked" into the radiator, it's "pushed" into the radiator. Such is the nature of relative vacuum.)
When you check a typical radiator cap, you'll note that there is a large flat rubber gasket and a silver metal "thingy" in the middle - that's the VRV.
You test the pressure seal with a pressure tester, and/or visually inspect the rubber gasket.
You then take a pointed tool (usually a knife tip) and GENTLY pry up under the silver disc to make sure it opens easily. It's pressed closed by system pressure in normal operation, and should open readily when you pry on it anywhere around its edge. DON'T PRY TOO HARD OR TOO FAR - or you'll wreck the cap and need another one. Usually, just the fact that I can get a knife point in there easily and it opens is enough for it to pass - you shouldn't notice any pressure needed against the cap, and there is a VERY light spring in there to hold it shut until pressure bears against it.
Make some sense now? If not, go get a radiator cap and re-read this - it will.
5-90