I think I've figured out what's happening, just not why.
I've used the highly scientific method of placing a food temperature probe on top of the radiators - great! All other factors being equal though, I think it's good enough.
All the radiators in the flat are registering around 48/49 degrees except the one in the living room. When the heating kicks in after a period of inactivity, that radiator reaches 48 and the room starts heating up but it begins to cool when the boiler's been going for a while - then it drops to about 38 or so and that's when the room stabilises.
Sounds like balancing?
So, my question is - given I don't have radiator thermometers to measure the temperature drop across all the ones in the flat, is the best thing to open them all and adjust them down 'til they're all equal?