The coolant system is pressurised so will always hiss when you take the cap off
Any way the price of the head from VW is around £1200 plus your labour has Jibba said thing is its not just the head that will need replacement, you'll need a new head gasket, cambelt kit and water pump, new seals and bearings, oils and coolant.
It all adds up and if I was in your boots I would be getting rid
Ive just ended up paying out £1500 to have the cylinder head replaced, on another note it does sound like fuel vapour unused diesel, also rather than the head it could be the EGR cooler thats leaking coolant into the exhaust which will give you white vapour cheap fix.
Darren