Ok, just had a good look at the brakes and I think the problem is that the brake cable may be tighter then the front brake cable, and so I can't pull it as much from the hoods (I normally use a couple of fingers instead of holding it full on).
Not sure whether that makes any sense, but simply I think it is because I can't get as much force on the handle and so the pads make contact but unlike the front brake I can't pull them tightly against the rims.... or I'm just going crazy?
I shall need to test ride the theory at some point.