I have found that using grosgrain ribbon is the easiest to work with. So I would first try using that kind. Also, I used this site when I first started trying to fold a boutique bow. http://girlythingsbows.com/boutique_bow.html
I now do a couple of things differently, but I still use this basic idea. Practice, practice and practice some more! I know lots of people on here talk about tuts and templates that they love. Do a search for the twisted boutique bow and that will give you some other ideas too!
As for the starching, I use spray starch from Wal-Mart (Stay Flo I think?) and mix it with water. It works well! I really like starching the ribbon before I fold because the bow folds better and holds its shape. HTH!