Done more messing around - I think it's purely down to how long it takes to get the return temp up. Boiler only really starts firing when the return temp is ~25°C delta to the flow setpoint (roughly might be +/- couple dregrees either side). I've been testing running the system on the UFH only and take anywhere from 1.15hr's - 1.45hr's to get enough return temp to run the boiler constantly. If I try to start the UFH + Radiators together, takes like 3-4 hours.
With the natually colder return temp from the UFH it just takes way longer to do this startup routine. am guessing it is fixed in the startup routine for efficiency wanting to optimise the condensing part of the boiler.
Only way around this I can see is to stop this "efficiency startup" routine. Have attached the screen it just sits on for most of the startup - it's on the "radiator only" setting. i'm wondering if the "hot water only" setting would ignore this startup and just run the boiler for me. Thats what i'm going to try next.
On start up all the boiler is looking for is that the flow temperature does not exceed SP+5C, (70C in your case), otherwise the burner will trip and the boiler will just keep doing repeated recycles. The (all) gas boiler(s) fire up at ~ 65% of rated output so 11.7kw, ideally, the boiler shouldn't exceed the SP,65C, assuming a flowtemp of 35C, (dT 30C), at start up then the flowrate will have to be, 11.7*860/60/30, 5.6LPM, Vaillants then maintain this 65% output for 60S (unlike other boilers which modulate after 10secs or so) so practically speaking you should have a flowrate of ~ 10.0LPM.
The minimum output of the 418 is ~ 5.0kw, assuming the flowrate is 5.6LPM, then the dT (at 5.0kw) is 5.6*860/60/5.6, 14.3C which you do seem to to be getting eventually.
These boilers don't have any "efficiency startup routine" but if the dT is ~ > 28/30C, just after start up then they will more than likely trip the burner and cause repeated recycling.
This is why I keep harping on ad nauseam about the pump flowrate, so you might, at the very least, just shut the discharge valve briefly and note the pump power, 21W will, theoretically, only result in a flowrate of, at most, 2.0LPM on speed III.