Sounds/smells like a leak somewhere in the cooling system. Have you noticed a coolant loss or a puddle under the car after it sits? Typically, pressure does not rise significantly in the system until after shutdown, but the combination of a completely sealed system and the proper water/antifreeze mixture should prevent boiling entirely. Other possibilities, unfortunately, include a blown head gasket or a crack in the head/block allowing combustion gases to enter the cooling system, which will cause bubbling. But that would mainly occur while the engine is running and most likely would also be associated with tell-tale white exhaust gases. The first order of business is a pressue holding test of the cooling system (i.e., apply external air air pressure using a special reservoir cap and see how long it holds after the supply valve is shut--done when the engine is cold).
Joel
'67 Lotus Elan S3 DHC (owned since 1970)
'17 Ford Focus RS