I have an Orion XS 1400 and a pair of SmartSolar 100/50 chargers in my RV, charging a bank of SOK 24v batteries with CAN communication. DVCC is configured to control everything.
Have you activated the limit charge feature though?
Excerpt from your link..
Limit charge current is a user-configurable maximum charge current setting. It works across the whole system, whereby Solar is prioritised first, then the Orion XS DC-DC battery charger and then the inverter/charger.
All I can do is confirm that my Wakespeed WS500 controlled alternator behaves the same once the batteries reach absorption stage, all charging is via alternator and solar drops to zero. At this stage of charging you are not at the CCL, but the CVL and the prioritisation does not seem to apply in this case.
Have you tried a really low CCL value so that this applies during bulk charging.
I’ve somewhat worked around this for now by creating a node red flow that turns off the DCDC unless my SoC drops below 90%. Unfortunately that makes it a hard on and off switch, not a nice smooth transition to the DCDC as my solar power drops off.