Be VERY wary of mentioning to your boss or the Chief Pilot/DO your thoughts about continuing in your current job and "pinch hitting" in the airplane...some managers don't look too kindly upon that as it 1. can set an unrealistic expectation in upper management for pilot duties & responsibilities and 2. could take away a full-time flying position.
Talk to the current pilots and tell them you want to make a shift into professional flying and see what THEY have to say about it.
If I were you, I'd keep the day job that pays the bills and will allow you to spend time with your new wife...and fly whenever you can to build your time.
This career is hell on personal lives AND marriages, and while I love to fly, I would never sacrifice my QOL and income to the level you would have to...with no guarantee of future success.
Good luck...