Interesting. Syracuse is a good school for an MFA, and those who know art will know that - so that's in her favor. Syracuse is also considered a solid school, overall, so that's also in her favor.
What she does next really depends on her interests and desires. But if, for example, she wanted to become a K-12 art teacher, the easiest way for her to make that transition would be to enter an MAT in art program, even though she already has an MFA. Get formal (and recent) teacher training, do student teaching as part of her program, pass the certification exams, and then try to find a job as an art teacher in the public or private schools. A masters degree in teaching would take her one year, and I have no doubt that she'd be admitted to a school somewhere.
If she'd rather teach art at the community college level, her degrees, as she has them now, are fine. What she would want to do in that situation is as you suggest - begin to build teaching related experience now, so she can put it on her resume when she applies for such jobs. She therefore may want to go to her local senior centers or Boys & Girls Clubs or YMCAs and volunteer to teach some classes. Once she has taught a few classes, she can begin approaching community colleges and the continuing ed departments of universities.
If she wants to teach at the university level, she needs to start exhibiting. She needs to build her credentials in terms of producing and showing her own artwork in order for her to be able to get a job at a uni.
And she can certainly do something that's either unrelated to her degree, or only peripherally related. She could try to get a job as a receptionist in an art gallery, or for a museum. In terms of the museum, she could volunteer as a docent first, and try to work her way to a paid job in that way. If she has computer and typing and admin skills, she could try to get a job - ideally for an arts related organization - as an admin. To get into that, she could first temp as an admin via a temp agency, for a while, to refresh her skills and to build a current resume. She could even try to get a job for a funky, somewhat artsy retail store, and eventually try to work her way up to some sort of management role, if she's interested.
She actually has a lot of options. Depending on which ones appeal the most to her, she'll need to do specific things to gain skills/refresh her resume, so she can get those jobs; but it's all possible.
Naturally, at least at first, when she's making her first resume, she should use more of a skills-based format, rather than a chronological resume. After all, she may not have held a formal, paid job for quite some time; but she has gained significant, career-related skills via her work as a housewife, and more of a skills based resume will help her to highlight those skills, highlight her strengths rather than her one weakness (which is lack of recent paid employment.) Since it's been a while since she's had to do a resume, you will need to help her out with this. Get a book. Go online. Find a resume format that highlights what's good, and doesn't emphasize what's bad, and use that.
As part of her job search, she should network the heck out of her contacts. Make sure that everyone she knows understands that she's looking for a job, and of which types. Church. Fellow moms. Fellow mom's kids. The guy at the supermarket. Her old real estate contacts. The places where she volunteers. Everyone.