I have experienced a similar type problem and it can get confusing until the valves operation is fully understood.
Assume the valve is in the rest position HW only. The valve has to move over to mid position and from there it has to move to CH only position.
The room stat provides power to 'white' wire. Within the valve it divides and feeds microswitches (1) and (2).
The feed through (1) drives the motor until it is activated at mid point. This cuts off the white supply to motor and picks up another supply. This other supply is provided from the programmer (HW OFF terminal) and feeds the 'grey' wire which continues to drive the motor to the CH only position where it is held against a stop.
There is also an alternative supply to the 'grey' from the satisfied terminal of the cylinder stat used when HW is ON (no need to consider this when problem is CH only)
So microswitch (1) has two power input sources feeding it, white for first half and grey for last half. There is just the one output to the motor.
Microswitch (2) is wired different, there is only one input but two outputs (not at the same time of course).
The divided white is the input and the initial output is fed to a pcb to supply a modified voltage to hold valve at mid point (not related to CH only problem)
Now the second output from this microswitch is the 'orange' wire.
This second microswitch is triggered when the valve moves beyond mid point, so it stop feeding the pcb (no longer required)and delivers 240 volts out though the 'orange'.
If this microswitch has dirty or burned contacts it can stop the boiler and pump from operating when in CH only mode.
It does not affect the other modes because HW is invovled and the cylinder porovides the power to run pump and boiler.
Of course if you have 240 volts on 'orange' when HW is off then valve is not the cause .