That being the case, I would go with the 135/91 job that gets you ME PIC. If you're in the 121 world, you are on the other side of things which makes it that much harder to make contacts in the GA world. With a 121 background, you *may* also have to deal with the "airline stink" that plagues some folks trying to break into charter and corporate.

If you're working in GA, then you will be familiar with doing everything yourself (flight plans, dealing with pax, logistics, etc.). This will give you a leg up on regional guys that haven't dealt with this stuff before.