Right, but just checking - before I start, should I completely let the air out of the expansion vessel, or does the air in there not matter?
I do advise letting all the air out before starting. This is because some water sometimes migrates to the air side and it is good to get that out first. It also gives an indication of the condition of the EXV.
Only then let the pressure out of the heating system and keep it depressurised as you top up the air to about 0.9 bar.
Tony