some vans seem to have been wired differently to the norm .
You can check the voltage of the B pillar socket etc, with either a plug in voltage device or a volt meter.
As you say when plugged into EHU the voltage should be 13.9 + Volts for the rear sockets (B pillar, C pillar & Tailgate). When unplugged from EHU the voltage should start to drop when using a 12v device (plugged in).
The front 12v socket located in the dash (location depending on dash type), should be connected to the starter battery , this can be checked as above. Starter battery should read IRO 12.6 volts or less when having sat for 60 minutes after driving.
You can verify the connection to the starter batter, via volt meter reading from the battery terminals. (Should read the same as the socket)
If you start the vehicle (when the starter battery voltage is less than 12.6 volts, the smart alternator should then start charging the starter battery , (voltage should show in range of 12.6 - 14.9 volts )
As mentioned above, some seem to get a trickle charge to the starter battery when on EHU.
This is an anomaly and not by design.
Any charge reaching the starter battery whilst on EHU will be small and probably only enough to maintain starter battery voltage.
The starter battery will naturally loose charge from day to day, for example If I am camping on hook up fro approx 4 days, i would expect the starter battery to be IRO 12.6- 12.9 volts at rest 60 minutes after arriving at a site, this then start to deplete , say for example I read the voltage after several days I would expect it to be IRO 12.2 - 12.5 volts.
If you leave it for several weeks the starter battery voltage will keep dropping to point where is will not have sufficient charge to start the van.
So long story, check the front socket / starter battery voltage to verify thd front socket is connected to the starter battery (I suspect it is)
If connected to starter battery what you described in post one is normal and purely coincidence , probably based on your starter receiving a trickle charge whilst on EHU when the leisure battery became full and went onto float when the USB device was removed from the rear socket.