Do I read your post right ?
When the engine is Hot with the cap fully closed the level is at around minimum. When you loosen the cap while hot, water rises in the expansion tank?
Does it actually overflow out of the cap? [Be
very careful loosening the cap when hot - nasty scolding water can fly everywhere unexpectedly

]
The coolant in the photo doesn't look as clear and clean as I would expect. I would get the coolant tested for hydrocarbons, many garages can do this, or you can buy a kit at a high street motoring store - or buy on-line. That would indicate or eliminate a head gasket leak with a high degree of confidence.
Other than that, I can only think there is an 'air-lock' (a bubble or bubbles) in the coolant system which compress under the pressure heat and a sealed cap, giving a low level. Then expand when the cap is loosened forcing coolant back into the expansion tank. These bubbles could be air somehow introduced during filling - or exhaust gases from a leaking head gasket.
Reviewing what I write, I'm afraid I'm tending towards a head gasket problem, but not 100% sure at all.