I've been trying to decide what I thought about Little M@tch Girl since I listened to it at the gym about an hour ago, and I think I've finally decided: I loved it. It wasn't my favorite Escape Pod story, and definitely not my favorite Escape Artists story, but it was very good and I enjoyed it a great deal. LMG was solid science fiction - a vision of a future gone awry, and depressing as hell. Some of the "plot holes" other posters are mentioning - the fact that the loss of the POV character's father's job was enough to scuttle her college hopes, the character's relatively blase reaction to the fact that her mother was still in there, somewhere, trapped forever - all make sense in the setting the story created and contribute to the bleak view of where we are headed.
To address those two points in particular:
Firstly, it's science fiction. In a world of rising college costs, it isn't hard to imagine a future where college is even more a luxury for the elite than it already is. If college costs more in the future and the character's interests aren't sufficiently "sexy" to attract the attention of a grant or a loan agency willing to take a risk on her, then she might find herself out of luck. The story did a good job of establishing that this is a future that's different from the now, and this is a difference consistent with the other differences the story established.
Secondly, I think the end of the story - the "Heaven" of Fl@me - was meant to have transformed the character's perspective to the point that her mother's plight wasn't as gut-wrenching as it would have been otherwise. It was sad, certainly, but not upsetting. Nothing's upsetting when you become aware of your part in the whole.
And that's the last point I want to make: I believe that the effects of Fl@me were meant to mirror the heaven of the original Little Match Girl. It's a pretty bleak trade - heaven for drugged out pseudo-bliss - but better than nothing, I suppose.