Vector Prime is a great book, and you're right about Salvatore, he is great. Vector Prime takes place about 20 years after Return of the Jedi, so there is a chunk of things that you'll be missing. You can get a lot of that stuff from Zahn's Thrawn Trilogy (Heir to the Empire, Dark Force Rising, The Last Command). However, if you can get past the fact that you won't know a lot of the new characters, Vector Prime is a good jumping off point, because it's the first book of the "New Jedi Order" series, and the beginning of a war that stretches over about 20 books.