So, are you saying that those two black wires are the call for heat from the UFH and the CH thermostat?
Not quite. When either of the two zone valves are active and in position, a switched live is sent down the orange wires.
One of the black wires that is connected to the orange wires in that terminal block will fire the boiler.
We don't know what the other black wire does, especially given the complexity of your system - it could be another pump connection for example.
But given your description of the UFH - it fires the boiler, but doesn't power the valve - a switched live from the UFH wiring centre is getting to the boiler somehow, and this may possibly be the place.
Assuming you haven't got a multimeter and you feel like experimenting; we could attempt to disconnect one of the black wires (with power safely isolated), and temporarily connect it to a spare unused terminal in the wiring centre.
If the boiler doesn't fire when the rad heating is called for, the disconnected wire goes to the boiler. Swap the wires back around.
If the boiler does fire when rad heating is called for, turn off the rad thermostat and see if the UFH thermostat still starts the boiler. If it does, then the UFH connection is somewhere else and put both black wires back in their original position.
Only attempt this if you are confident you understand what I'm trying to suggest!