Aye, I think I'd be tempted to disconnect all wiring relating to DHW and concentrate on getting just the CH working as it should then concentrate on the DHW a bit at a time testing as you go.
If you try to look at the whole thing at once you can end-up not being able to see the wood for the trees, so break it down into smaller more manageable bits.
And remember; when you're up to your ar$e in alligators it's difficult to remember that your first priority was to drain the swamp.
I agree re it's sometimes quicker to just disconnect and reconnect, but to answer the other question if you connected the cylinder stat backwards it would make connect on fall rather than rise so that wouldn't be the cause of the boiling water.