(The situation's completely different if I do know you - candidate referrals from personal networks are always fine.)
You can help her by giving her the confidence that it's possible for a non-technical person to hustle their way into a startup and then learn a ton. You might also be able to help her by doing research on the startups, to identify candidates she wants to approach.
That said, the main things that are going to make the difference all have to do with her and her attitude. When I've hired people in your girlfriend's position, enthusiasm, confidence, hustle, and the ability to genuinely convey knowledge about and interest in my company and industry have gone a long way.
When entry-level jobs are publicly posted you get a deluge of people, and it's hard to stand out. Instead of applying to what's out there, I'd be approaching companies that haven't bothered to post. A personalized email that included feedback on / ideas for / questions about my company, a description of what she could do for my company now and what role she'd like to grow into, affordable salary expectations, and a request to talk further by phone would certainly get my attention. Done right, I'd think about whether I had a role for this woman, even if I didn't have an open position.
I've got an (anecdotal) impression that things are a little tight in NYC right now for entry-level folks - a former intern of mine with experience at multiple startups has put together some part-time work, but she's been looking for that full-time position for months now. I wouldn't let that discourage your girlfriend, though - work hard, long, and smart enough and good things will eventually happen.