I’ve got a PMS3H with a CTEK 250sa charger (it came with a split charge relay, which I changed very soon after getting the van).
The way I use mine:
if it’s parked up, not being used, the battery selector is off.
if I’m camping without hookup, it’s set to ‘van’ which is the Leisure Battery on mine. (I’ve renamed it Leisure with a label maker)
They recommend turning the battery selector to ‘off’ when driving, but I’ve driven with it on.
if I want to use the vehicle battery as an alternative to the leisure battery (not advised, as you may flatten it and not be able to start the van) I set it to ‘car’ (now labelled starter).
I leave the ‘charger supply’ off unless I’m hooked up to the mains and want to charge the leisure battery. If I put the battery on ‘van’ (Leisure) and the charger supply on (when hooked up), the mains charges the leisure, which runs the camper electrics. I can charge the starter battery, by plugging the mains in, charger to on, and ‘car’ selected on the battery selector (although I don’t do it)
The ‘pump’ switch just isolates the 12v for the tap. I tend to turn mine off if the tank is empty, to avoid accidentally running the pump dry.
As for whether your van charges the leisure when driving, it should do. Look for a 12 DC-DC charger, or potentially a 100A relay somewhere near the leisure battery. Switch to leisure battery. Now watch the LED battery meter and get someone to start the van. The LEDs should indicate a voltage increase. Alternatively use a multi meter.
Hope this clarifies!