Hmmmm, sounds like a water pump issue to me.....
Water not being pumped around the engine, gets to hot, boils, pressure increases in the entire system, and comes out of the emergency pressure release.
When was the cam belt done? It must be an AGU engine as it;s an early motor - done reasonable miles I'd imagine, most likely 100,000 plus, meaning belt change at a likely 60,000. Water pumps on the 1.8T notoriously flaky...
Did you have water temp issue leading up to this and it's got worse over a period of time?
What temp does the water get up to on the dash (since you say it's overheating)?
The radiator valve, if broken would just leak the water out all the time IIRC, it's a most useful tool for draining coolant from the engine!