you can safely use 95ron fuel in a 91 GTI, because they have a knock sensor which allows the ECU to retard the ignition timing when the engine starts to knock. You'll just loose performance!
Check out my digifant tuning guide in the maintenance section, check the timing as organisys said, and also look at the idle switch to make sure it clicks when the throttle is closed. Also make sure the knock sensor is present and connected, its bolted to the front of the block.
If it looks a bit dodgy, this may be the real reason the engine has blown its head gasket if that turns out to be blown!