I suppose the hot pipe is on the trv end(the thermostatic valve) depending on which make the valve should be easy to take off open it fully there should be a plastic fitting under the valve should turn off with your hand or use small grips to crack it open this will leave u with the valve to...
Under boiler if you follow cold mains into boiler there will be a isolating valve to turn of cold feed into boiler. which come with boiler,if not turn off via stopcock into house this will isolate cold feed into boiler.Drain hot via lowest hot tap, close iso valves on flow and return drain...
Good idea but dhw wires to short if you could get some small crocodile clips to extend to ch as ch wires long enough with a small pull just release small black clip restrictor.
How long boiler been installed, sounds like thermistor on way out,to test drain off enough water out boiler, isolate cold mains open up hot tap till drained swap dhw thermistor with ch thermistor , turn on mains then pressurize system see if it stays on,or run hot to see if cools.
Change diverter valve wax capsule but make sure you get new seals as old ones just crumble £84 hrp at plumb center if can afford whole diverter assembly just go for it easier to fit whole lot.
If the flow is getting to hot to touch but some heat is getting to some of the rads but luke warm the problem,to me as i have just repaired white star recently is the small heat exchanger at the rear of boiler cost £112 plumb center.
Have any rads got a drain off on ,if so attach hose to this with jubilee clip and the other end to outside tap turn on slow to push air to header tank this will alleviate the problem.
Have u got lockshield valves on both sides if so close both down pace small container under one side take rad of drain into a bucket test valves one by one see if they are working if they are clean rad and replace
Take thermo top off so you expose valve spray wd40 leave for minute then with srewdriver press the small brass thing in middle up down to release valve.
drained boiler to add new rad ,filled up boiler ,switched on. pump turning fan kicked in, no ignition, pilot stays, on same on hot water.turned of from wall all light sequences are as in manual, but boiler does not ignite.