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My car has 205/60/16R tyres on it. I have just had two new front tyres put on and the tyre guy told me to maintain the pressure at 36. On the door pillar it has a label that has KPA and Kg/cm2 and in the columns next to the particular tyre size 220 and (2.2) and I don't know how to interpret this. I always used to maintain about 30 when I visit the service station just down the road so 36 sounded really high. How do I know if what I have been told is correct? How do I interpret what the label is telling me?

You don't say what type of car this is, but 36psi would be a little on the high side for most mainstream cars. 30psi would be closer to the norm, although slightly low.
The label stating 2.2KPA (which equates to 32psi) would be the approximate recommended pressure for most mainstream cars, and this is the pressure I'd recommend for you to use.

2003 Nissan Primera S/W with no tow bar. So sounds like 32 will be what I go on. I check them every week/couple of weeks.