In each situation there are two essential requirements (a) how to get the valve to the correct position and then (b) how does the boiler light.
With HW only it is fairly simple. No power on the 'grey' wire and no power on the 'white'wire. The return spring unwinds the motor so valve is at HW.
The boiler lights because HW is switched ON (and in demand). The HW ON wire feeds the cylinder stat which fires the boiler, until its satisfied.
If we jump to CH only it's a bit more complicated. Say valve is at HW position, but HW is not switched on. Its done in two stages with two power supplies.
First stage. The CH ON wire feeds the room stat, this in turn feeds the 'white' wire of the valve. This drives the motor until it triggers micro switch No 1.
Second stage. There is a HW OFF wire and this feeds the 'grey' wire of valve. (this is live because HW is OFF). The triggering of M/S No1 is just switching power from 'white' to 'grey' at midway so the valve can continue to CH only.
In this situation there is no HW or cylinder stat involvement, This is where another M/S No 2 comes in. During the second stage this M/S No 2 is triggered. This allows power (which also comes from the 'white') out through the 'orange' wire to light the boiler.
When CH is satisfied, the room stat cuts the power so boiler stops, but valve does not move, cause its not the 'white' thats keeping it there it's the 'grey'
Now for the most complicated.
When HW and CH are switched ON, it does not automatically mean the valve goes to mid position. It all depends what is in demand and what is satisfied.
The valve moves according to the demands met.
If HW satisfied valve moves to CH
If CH satisfied valve moves to HW
If both are in demand valve moves to middle.
Looking at these three positions, the last two involve HW and cylinder stat lights boiler, but it relies on the M/S No 2 for CH only.
Also if both HW and CH are in demand and valve is at midway and CH becomes satisied before HW (can't see it myself), the room stat would cut off 'white' supply and valve would go to HW only
When both HW and CH are in demand the radiators get a share of the water. (boiler lit by cylinder stat) As soon as HW is satisfied (boiler stops)its supposed to move the valve to CH and re-ight boiler (by M/S No 2).
In some cases the valve does not move to CH and in some cases it does, when it does and boiler does not light it points to M/S No 2 being at fault.
There appears to be some doubt regarding the wiring. or is it more misunderstanding. Don't know?
sorry for a long winded episode, just thought it may help to clarify things.