So from your results:
White wire 3 port valve at H with no programmer demand 0 (zero) volts
This voltage on the white wire is what it should be. Without heating demand, there should not be any voltage applied from the heating controls to the motorised valve to open the heating port. But as you say, it is open!
Orange wire 3 port valve stuck on H with no programmer demand 115v
That's a bit high. This is the wire that provides the live from the motorised valve to run the boiler, and should ideally be quite a low figure when neither a heating or hot water demand is present. Voltages do appear and they vary from system to system, probably because of being fed back via the boiler's circuitry. Based on that, I tend to agree with the post from D Hailsham:
if you have a multimeter (and know how to use it), check the voltage on the orange wire when CH is On (240Vac) and Off (50-150Vac). If the Off voltage is higher than 150Vac the problem could be the valve. If below 150Vac, the boiler is probably the problem.
Once the valve has moved to the heating only position, the orange and white wires are connected by a switch inside the motorised valve. I suspected that some voltage from the boiler is fed back via the orange wire and through the switch was sufficient to keep the valve open. BUT, the bit I can't get my head around, is that if that was the case, the white wire which is now connected to it would also be at 115V and it isn't. So, I'm tending to think that it may be the valve.
Personally, my next step would be to 'bench test' the motorised valve actuator. If you are competent and can do it safely, it's not too difficult. I have a little test rig with a switch for each of the inputs (White and Grey wires) and connect my multimeter to the orange wire to show when it's 'on'. By switching the white and grey wires on and off, it's easy to check that the valve position and the output from the orange wire are as they should be according to the table below:
Your other results below look more or less OK, I don't see anything obvious:
Orange wire 3 port valve at H with CH programmer demand 115v
That's low if the room thermostat was also calling for heat. But it's not low if it wasn't, in which case would expect to see the same voltage as the previous result (115V)
Orange wire with 3 port valve at mid position with demand from programmer for hot water and CH 250v
That's as expected as the HW cylinder thermostat will be providing it from the hot water control side.
White wire with 3 port valve at mid position with demand from programmer for hot water and CH 250v
That's as it should be, same as above. White and orange wires now connected via internal microswitch.