Did you conduct that experiment with both HW and CH calling for heat, or one of them, or neither?
It suggests to me that possibly at least one of those two valves is stuck, or one of the microswitches therein is welded closed.
I guess the next experiment is to find out which one is the problem. If you ensure neither HW or CH is on, and then repeat the disconnecting experiment, do you get the same result? You might hopefully find one valve disconnected turns the boiler off, but the other doesn't. It would be the one that doesn't that's the problem (or something in that circuit?)
It suggests to me that possibly at least one of those two valves is stuck, or one of the microswitches therein is welded closed.
I guess the next experiment is to find out which one is the problem. If you ensure neither HW or CH is on, and then repeat the disconnecting experiment, do you get the same result? You might hopefully find one valve disconnected turns the boiler off, but the other doesn't. It would be the one that doesn't that's the problem (or something in that circuit?)