Switching the temperature up and down or on and off needs the lock shield valves set very well, or needs eTRV fitted. I have the latter, but would not sing their praises, of course house design is also important, so there is no one system fits all, however the standard system is.
The boiler sends hot water around the system and measures the return temperature and adjusts flame height to suit, the return temperature of the water is controlled by the lock shield valves and the thermostatic radiator valve, when the return water is too hot the boiler turns off, after a set time it turns on again, plus some anti-cycle software in the boiler that adjusts that set time.
You may note no wall thermostat, in theory not required, in practice however often they are.
When a timer turns off the heating all TRV will in time open, so once the timer turns on again all radiators want hot water, now if the lock shield valves are set correct every room will start heating, if not rooms may be heated one by one. However once every room has hit the set temperature the lock shield valve setting has little effect. The TRV has taken over control.
So likely it is more efficient to keep it on 24/7 because you can tweak each TRV so each room is exactly the right temperature, where if switching on and off it's far harder to set the lock shield valve to work A1 at reheating the house in an even manor. However not sure what theory says?
My problem is sun and wind, the direction of wind, and if the sun is shinning or not changes how much heat is needed in the two down stairs rooms, odd but not noted a problem up stairs. I have tried all sorts to stop the main living room getting either too hot or too cold. Nothing seems to work in the house I am living in now.
However old house simple programmable thermostat worked nearly A1, simply down to when the sun comes into the windows. The bay windows in house I am in now I am sure are the major cause of the problem.