unfortunately it sounds like a HG issue...
i too was very cautious of my temps, but never let the engine go above 100C (and i was just guessing as to where 100C was on the gauge... i knew at which point the expansion tank registered 87C and used the reference point on the gauge to judge when i should ease off the pedal)
i had a faulty t-stat... it was only opening very little... so it could not cope with the amount of heat generated from highway driving... very very annoying! but my coolant system was pressurizing normally... at 100 deg C you must realize that you are basically creating a mini steam engine, and 20 psi could easily be reached at that point.
i would flush the entire cooling system... it sounds to me like your heater core is plugged up, or has an air lock in it...
one good check is to run the engine with the cap on from cold, and take the cap off at 1 min of idling... it should not have built up much pressure at all... if it has, then you are heading into hg territory
