All I can say is that it worked when installed. I will try to explain how I got there:
First of all don't forget what I said regarding the diagram:
djsmith83, when I get back on my laptop tomorrow, I will revise the diagram for your application. I'm not going to attempt it on a tablet. Who know what it will end up like.
1. When hot water only is set 'on' (5) and (6) are connected together by the Nest. (6) is connected to the live, (5) becomes live and so the boiler and pump operate and pump hot water only around the hot water cylinder. The radiators don't heat up because the motorised valve remains closed.
2. When heating only is 'on' (2) and (3) are connected together by the Nest. (2) is connected to the live, so (3) also becomes live and the motorised valve opens. As hot water is not required, (4) and (5) are connected together by the Nest (4) is connected to (3) by a link, so when the heating comes 'on' (5) also becomes live via the heating section of the Nest and the pump and boiler operate. This is the 'fly in the ointment' bit, because as the boiler and pump need to run for the radiators, the hot water will also heat up. But this is because of the plumbing restrictions. Wiring it like this avoids having to check that the hot water is set to be 'on' at exactly the same time as the heating. Selecting the heating 'on' also selects hot water 'on' for you automatically.
3. When heating and hot water are 'on' (5) and (6) are connected together by the Nest. (6) is connected to the live, (5) becomes live and so the boiler and pump operate. Also (2) and (3) are connected together by the Nest and the motorised valve opens. Water is thus pumped around the hot water cylinder and also the radiators.