Sorry, I'm still not exactly sure what you want to do. ajax.php actually returns some html (which in a way can be thought of as xml), and the javascript uses it to set the innerHTML property of an element. I suppose there isn't any reason that you couldn't return <user> or other custom tags, but then you'd need to process it using javascript. It's probably easier to format it as html (using templates if you want) if that's how you're planning to display it.
Maybe I'm still missing the point of what you're doing. If you want to make a plugin that returns user data as xml, that's fine, but it doesn't have anything to do with vbulletin templates. How do you want
http://localhost/upload/misc.php?do=xml to be used? What is going to request that data?