Final Update: The switch next to the back door stopped working as it happens that that socket is on a circuit of its own - which was labelled on the CU as 'Water Heater'. So, I can only guess that when the water heater that used to be in the kitchen was disconnected and the combi boiler was installed, the previous owners just stuck a plug socket on there. When I switched off the MCB labelled Water Heater, I didn't realise I was actually switching off that one socket - and the timing of that socket being switched off at the CU coincided with me removing all the water off the flat roof, and so the two things happening at the same time made me believe they were linked.
After a few more trips, and RCD instantly resetting - it eventually gave in and didn't actually reset, which gave me the opportunity to actually start unplugging items around the house until it stayed on. After all this, turns out the freezer is the problem. Unplugged that, and the RCD held, and then after a few minutes I plugged it back in and the RCD tripped almost immediately. Unplugged it, reset the RCD and left it an hour, all stayed on, plugged in the freezer and it tripped again. Brought the party freezer in from the 'garage', transferred all the food into that and left the freezer unplugged - and we're now on the 8th day without a trip, so I think (touch wood) I'm out of the woods!
Thanks again for everybodies advice and help.