if you are getting both heat/hw but only when the hw is on to sounds like a seized spindle or jammed actuator.
If the OP is getting CH and HW, the valve must be opening to mid-position. The boiler is supplied from the HW stat in this case.
If CH is ON and HW is satisfied or turned off, the valve moves to CH only open and the boiler is supplied from the orange wire. If the valve can move to mid-position, it's unlikely that the valve will not move to CH only.
However it is still worth checking the spindle can turn - it won't be a complete revolution, usually less than 90°.
If that's OK we have to find out if it is the actuator or something else.
Turn off power when connecting/ disconnecting wires This usually means unplugging the lead or removing the fuse from a spur.
Disconnect the valves Grey, Orange and White wires (
make a note of which terminal they are connected to)
Turn CH OFF and HW ON
Turn HW stat up - boiler should light
HW pipe only from valve should get hot
Turn HW stat down - boiler should go out.
This confirms the Call side of the HW stat is working.
Connect the White wire to a permanent supply.
Turn CH ON and room stat up
Turn HW stat up
Boiler should go on
HW and CH pipes from valve should get hot.
Turn HW stat down
Boiler should go out
This confirms if valve is working in mid-position
Turn HW and CH OFF and set CH and HW thermostats to low
Connect grey wire to a permanent supply
Reconnect the orange wire to its correct terminal
Turn CH ON and CH stat up.
Boiler should light and CH pipe get hot
Turn HW ON (leave HW stat low)
Boiler should continue to run and CH pipe get hot.
This confirms if the valve is working in CH only
Reconnect White and Grey wires to the correct terminals.
If it fails any of these test the fault is in the valve actuator.
If it passes the tests, the fault lies elsewhere. Either the programmer or the HW thermostat.