I like the look of these vests too... I can imagine they would help in re-training your back etc to stand up straight. My problem is that I have always slouched - it goes back to being tall, which I hated as a child (be bigger than all the boys etc). My back muscles are therefore not developed enogh to hold my back up straight, no matter how hard I try. I regularly notice myself slouching and pull myself up into the correct postion. I can't hold it for long though and it's pretty uncomfortable.
I would love to try Rolfing or something similar but as a student I quite simply can't afford it...