Made this exact jump last year — best decision I made for the van build tbh.
Few things worth thinking about:
The parallel switch idea — I've seen a few people do this but it makes me a bit nervous. You're essentially connecting two different voltage systems momentarily which can work, but if your 24v bank is sitting at say 25.6v and the 12v start battery is at 12.4v the current rush isn't ideal. Worth adding a resistor or a proper battery combiner relay rather than a straight parallel switch.
Alternator charging — how are you planning to charge the 24v bank from the alternator? This is where most people get stuck. I went with a Victron Orion-Tr Smart 12|24-15A DC-DC charger and it's been rock solid. Isolates the systems properly too, so no voltage mixing headaches.
Battery choice — I run Fogstar Drift 24v LiFePO4 now and the efficiency gains over my old 12v setup are genuinely noticeable. Less cable losses, smaller wire runs.
What's your current 12v start battery — a standard lead acid? If so the aux start parallel thing might be fine as a backup emergency option but I wouldn't rely on it as primary charging path between the banks.
What inverter are you running? That's usually the thing that forces people to 24v in the first place 😄
Would love to hear what others have done — especially anyone running a split charge relay setup between the two voltages. Surely someone's cracked a cleaner solution than I have.