The phone only has one wireless radio; it can only be active on one provider at a time. If you're on a call on provider A, the phone cannot talk to provider B at all, even for data.
Enabling WiFi calling allows the phone to operate on provider B's network through A's data connection while you're on a call on A, the same way it would over WiFi when you have no cellular coverage. This gets around the limitation.
Why would you not want to enable WiFi calling? It's free and improves your coverage if you're on WiFi in places like deep in buildings.