If there's exhaust getting into the cooling system, it would be pretty noticeable on a cold start. If you start the engine and hard rev it for a few seconds, then check the coolant cap and it blows off on a cold engine, then there's likely a problem with your head gaskets (well, not every time). If you left the cap off while the engine was idling and warming up, maybe it boiled from the fact that it had no pressure? Exhaust gas doesn't make it boil necessarily, it makes it puke out because of the gases pushing it out of the cap, that's why it will do it cold. If the engine was overheating from a bad head gasket, you would probably know pretty quick just from driving it around.Just flushed the hell out of the system. Fired up the car and let it warm up. Before it was even mid-temp range the reservoir started filling up and boiling out. I still don't see any issues with the water pump.
I guess it's probably the head gasket? Dammit. That sounds like a huge job...
Is it possible that you just had a bubble push itself out?