JFBConnect creates standard Joomla users, which Virtuemart, or any other extension, can use like normal. There is currently no additional integration with Virtuemart though, so a user created would be just like a user that's created by going through the normal Joomla registration flow. There are many sites that use JFBConnect and Virtuemart together, so this may not be an issue for you, but tighter integration (where we pull a users Facebook information or add them to a specific shopping group) is not something we currently do for Virtuemart. We already have the profile import integration for JomSocial, Community Builder, Agora, Kunena, and K2, so if you're using one of those extensions, you can import the user's information there and Virtuemart may be able to take advantage of it already.
As for adding the actual "Login With Facebook" button to your current site, that's very simple. All you need to do is add the text {JFBCLogin} to wherever you want the button to appear, and JFBConnect will place it there. This can be in your existing VirtueMart login module, in an article, or in a custom HTML module. That's in addition to our own JFBCLogin module, which is basically the Joomla login module with the additional button.
Hope that helps!
Alex