Just heard back from PRS Customer Service (Thanks Matt!).
As I thought, the pairs of jacks are in parallel, and if I wanted to add an external cab I would move the 16 ohm internal speaker plug to the 8 ohm jack and then plug in a 16 ohm ext cab into the other 8 ohm jack.
i.e. speakers are parallel, total load should equal 4 or 8 ohms if using those pairs.
If I had just a single 8 ohm speaker, I would plug it into one of the 8 ohm speaker jacks (presumably not the one that says EXT, though I don't know if it really matters).
So I notice that PRS 2x12 cabs are always 8 ohm (at least, all the ones I have seen, both on the PRS site and in used classifieds etc), whereas the 1x12 is 16 ohm. And the 4x10s are 8 ohm, while the 4x12 is 16 ohm.
Obviously the 2x12s are therefore two 16 ohm speakers in parallel, and there is no way to reconfigure that to a 16 ohm load without swapping speakers.
Anyone ever come across a PRS 2x12 that was 16 ohm?
I suspect I'll be getting a 1x12 extension cab. Eventually...