A catalytic converter is supposed to operate under a fairly narrow range of conditions. Right temperature, right mix of gasses out the pipe, not too much uncombusted hydrocarbon. When the thermostat sticks open, the engine doesn't reach operating temperature promptly, or in winter, at all.
The engine sensors see a cold engine, and richens the mixture until it warms up - which never happens. So, too much hydrocarbon goes into a cold CAT, isn't catalyzed, and it clogs up. Worst case, if you get too much gas back there (as when the engine misfires), it combusts in the cat and ruins it in minutes instead of months. In the case of my car, running through a winter with a stuck thermostat cost me a CAT, plus more clogs in the PCV system, higher fuel consumption, etc.
In your case... if your NOx is high, you have a lot of possibilities. It may be a bad or incorrect CAT; not all setups work with aftermarket CATs. The fact that you have to trick the rear sensor means you have a real problem. More likely, though, are a lean fuel condition (from vacuum leaks, clogged PCV system, bad MAF, etc) misfires, exhaust leaks, or even a bad forward O2 sensor.
Unless you're throwing P0300 series codes from misfires, coils or spark plugs won't fix it.