I have been trying to configure my boiler wiring, the only way is to draw it out, then consider the logic will it do what you want. My problem was the original system used the switching of a pump to select domestic hot water only, domestic hot water and main house heating, and domestic hot water and flat heating, and all running.
It has been found the water flows in reverse direction in other central heating system once a pump starts, and once heating pump turned on it will continue with thermo syphon when turned off again. So plumber is due to fit motorised valves, but even then we can't turn off domestic hot water if central heating running, and when only domestic hot water is required the only control is the time the boiler runs for, found one hour a day is ample.
However I have one big advantage over you, I am using Nest which has the com, N/O and N/C for central heating and domestic hot water not connected to mains, so I have DHW common feeding the boiler and N/O has line feed, and N/C connects to line through the micro switch in the motorised valve.
But without drawing it all out I would have never followed it.
So I started with a photoshop image of pumps, motorised valves, heat link, boiler and thermostat and wired it as I thought it would work, then constructed a truth table and coloured wires red for each option to see what would happen.
So first some safety considerations to ensure nothing burns out.
1) If micro switch in motorised valve fails will a by-pass valve open?
2) If you turn off boiler, is there some where for the heat already in the boiler to go?
My system fails on first count, if micro switch sticks the pump will likely cavitate, I am taking a chance as simply no room for by-pass valve, the second is OK as domestic hot water is thermo syphon so any heat in water on switch off will heat domestic hot water.
So truth table.
C/H main house off, C/H flat off, DHW off = boiler off.
C/H main house on, C/H flat off, DHW off = boiler on, C/H main house on, and DHW heated anyway.
C/H main house off, C/H flat on, DHW off = boiler off, flat will not be heated.
C/H main house off, C/H flat off, DHW on = boiler on and DHW on.
C/H main house off, C/H flat on, DHW on = boiler on, C/H flat on, DHW on.
C/H main house on, C/H flat on, DHW off = boiler on C/H main house on, C/H flat on, and DHW heated anyway.
C/H main house on, C/H flat on, DHW on = All on.
So you need the same truth table for your system, and if there are manual valves then consider what happens if a valve is not turned off or on when you change over, as the system gets more complex then there comes a point where a PLC may be the best option, but in essence the Hive or Nest is a PLC or building management system.
One option I have missed, is if the immersion heater is switched on what happens? Specially if boiler turned off for example because of low fuel levels. In my case the FCU switches off all pumps and motorised valves, so there will be no flow through central heating, however the original set up had three FCU's so the pump could be run without the boiler, as to if the pump could suck hot water from the hot coil and heat the radiators with it I never tried.
I think if I was designing your system I would be using motorised valves to switch between the two boilers and would use the built in micro switches to ensure all swapped over.
So this is my system
you need to draw out some thing similar for yours. As to if my system works I don't know, as yet still waiting for plumber, but it works good enough with a bridge wire, until plumber has done his stuff.