As far as opening the degas bottle cap, that's like opening the radiator cap on an older car. Don't do it when the engine is hot. It is NOT an overflow bottle like you find on other cars. Totally different style of system.
Note that ANY time you open EITHER of the caps in the coolant system you allow air into the system and MUST re-bleed. Also, check your coolant level when the engine is cold - you're probably low from opening the degas, the water expanding, and rushing out. I'm surprised you didn't get burned! The coolant should be between approx 210 and 230 degrees once the engine has warmed up. Especially at the degas bottle, which is on the hot side of the system.
There's a H crossover in the exhaust, so the blockage can be anywhere in the pipe, but I would expect after the crossover, which means the mufflers.
If a cat is clogged you'll have other problems, like horrible gas mileage, poor performance, etc.