As gucciman says, there could be an underlying fault causing the valve to open, if it is the expansion vessel, then you are looking at an expensive repair.
I had exactly this problem on my boiler and it was only the valve. If the boiler pressure is reading low, then the value should not be open. If you are able to pressurise the boiler and get it going, keep a close eye on the pressure gauge.
A pressure relief valve will cost around �15 and should take a novice less than an hour to fit (although on some models, access is limited). Call out a repairman and the sky�s the limit.