Well....I guess it gets better in some ways and not in others. The nice thing about instructing is that you set your schedule. That is about it as far as I am concerned. Not too many people enjoy it, they just see it as a way to get to the next step in the food chain.
As far as my QOL getting worse...I used to fly corporate before the airlines. Had a set schedule, good pay, great aircraft, etc. There wasn't much outlook for advancement, and maybe like your husband, the grass looked greener on the airline side. Thought it would be cool to fly bigger and better.
It was exciting for the first year. New enviroment, new plane, new people, new type of flying. Then I realized that it is all the same, day after day, just like instructing was. Now the bad part is that I don't get to make my own schedule anymore, and since you will likely spend several years at the bottom at most regionals (not much movement upwards but it goes in cycles), that means lots of working holidays, missed functions with my kids, and odd days off when everyone is in school or at work.
Second, the airlines are an unstable beast by nature. Once you stay long enough to get a "line" and somewhat of a decent schedule, changes in management or the industry can send you right back to where you started, or worse, put you on the street (take 9/11 for example).
My company is constantly adding and deleting flying thereby growing and shrinking the size of our bases. What that means is that the poor guy at the bottom, who is finally living where he wants to live now and bought a house, is displaced to another base only to commute until a spot opens up in his chosen base agin. All of this for pretty crappy pay. Better than instructor pay, but not very good pay in general. When you get more senior, you worry about all of this less but it is always looming. That is just one example.
Once you have been somewhere for awhile and become a senior FO, life can be pretty good. However, the minute you take an upgrade opportunity, there you are at the bottom AGAIN! All the same worries and hassles. Sitting on reserve and away from home most of the year and used and abused by your schedulers.
Speaking of schedulers, and I don't want to get too deep because if you haven't been there it might not all make sense, you have to CONSTANTLY cover your ass with respect to the regs and the FAA. Schedulers are taught to wring every little hour they can outta you and then some. If you aren't careful, you will be breaking required rest periods and overflying yourself. Well intentioned, but illegal.
I missed corporate flying immensely once I got here. I had a good gig, but I think in general, it lends itself to a whole different lifestyle. Granted, there are plenty of crappy corporate jobs out there too, but there are so many to chose from that it gives you more of an ability to determine what your QOL will be (such as how often you will work or how many RONs you will encounter per month). Also, I can't say this for sure, but from my own experience corporate pays better.
As far as getting jobs goes, I don't know where you are and how populated it is, but exposure and go-getting is my suggestion. I met one guy who introduced to me another and so on and so on. If your hubby isn't too social, he will probably have a hard time doing this, so maybe he should invest some time into learning these type of skills in addition to his flying. I don't know how you LEARN to be social though. Certainly I would flood any corporate office (with aircraft) with my resume and make many followups.
Also, if you guys can afford it, I would ***** myself out for free. I think this is total BS, but it is a good way to pick up right seat flying and then develop relationships with whoever is in the left seat. This is how I got my corporate job.
Other than that, my only suggestion for getting into corporate flying is to meet the minimums with good quality flying. The sim thing isn't a dead-end thing by any means, but he needs more actual flying. In that year it would take him to get his type, he could have built up another 1000 hours and only 25 more multi hours will likely open the door. A type rating with no time in the aircraft will probably not help him as much as the 1000/100 will. You also have to keep in mind that insurance is often a corporate stumbling block.
OK, one more thing. Consider flying cargo. They seem to really be hiring right now and, like with corporate, you have more to pick from with respect to they type of flying you will do and when you will be doing it.
Hope all of that helps!