Replacement of one control for another (eg to fix a fault) no MWC required.
Any new wiring or the addition of a new control (eg adding a roomstat) then an MWC would be required and the work is notifiable to LABC under Part P (See App Doc P, under General Guidance, Additional Notes, item n on pages 8 & 9).
If you completely rewire a CH system (eg new boiler and conversion from gravity to fully pumped) then a certificate is required. In this instance it is debatable whether the cert should be an EIC (new sub circuit from FCU out) or MWC (sub circuit added to ring). I'm in the latter camp.
Of couse, you cannot test IR at 500V due to risking damage to PCBs etc. Neither can you measure R1+R2 due to needing the system to be live to switch relays etc. So, measure IR at 250V and measure R2 at all points (from the earth at the FCUor wiring centre) and check Zs at the FCU or wiring centre. Record these on your cert with notes about the limitations.
Note that if you are doing the wiring for a new boiler install, then there is no need to notify via your scheme. This is because the boiler install is notifiable (which the plumber will do) and this notification includes associated electrics.