The increased pressure raises the boiling point of the water.
Additional waterpump pressure only occurs within the engine castings, there being a deliberate restriction located at the cylinder head water exit point. This allows the water in contact with the combustion chamber and exhaust ports within the head to resist flash boiling into steam bubbles.
These high temperatures are very localized, so the superheated water quickly mixes to a lower average temperature with the bulk water flow through the rest of the cylinder head.
Average cylinder head water discharge temperature is therefore no real indication of the peak temperatures reached in various critical hot spots within the head.
The rest of the cooling system external to the actual engine is also pressurised, but only to typically 12psi. But here the water is well mixed and the conditions for boiling much less extreme.
Over the years many racers have discovered that removing the thermostat totally, can lead to overheating. The theory being that the water travels too fast through the radiator to cool properly. That is simply not possible.
The real reason is flash boiling within the cylinder head which can very quickly lead to pre ignition, cracked heads or force a lot of water out past the radiator cap.
Once steam bubbles form they grow rapidly and can self sustain. Only backing off the throttle will save it.
If it has to survive more than a couple of seconds of flat out full throttle load at high power, the higher the internal water pressure within the head, the safer it is going to be.