For John the Boilerman...
If the motorised valve were in the wrong position - i.e. set to drive water around the radiators - the boiler would still recognise a call for hot water in the storage tank and attempt to staisfy it and fire up - the radiators would get warmer and warmer irrespective of the central heating controls.
There is no report of radiators being too warm but only the boiler not firing when the programmer is calling for hot water. It's unlikely, therefore, that your diagnosis is correct.
Peccavi's friend, March 2009