Thanks for all the advice guys. The removal of the grey wire allowed me to test turning on HW with CH on or off. As this worked it meant HW off what always being triggered. Testing the voltages on yellow/green (from Nest) and blue from boiler stat I found yellow/green always 240V regardless...
As per advice above I removed grey wire and HW works on demand. I subsequently got the voltages of Blue and green/yellow when disconnected and the green/yellow from ter 4 in Nest constantly has 240V.
It's busy I know...
Black cable is valve, white on right from boiler, pump cable comes in from left and in from top is power, boiler stat and wires from nest, thanks.
The only way I can get HW on is to turn off the heating at the fuse, thus resetting the valve to the default position. As soon as I add CH, HW gets turned off and even when CH reaches the optimum temperature and HW on, it still does not come on only a fuse reset will do this.
I have a newly...