XML (as I see it) is more for times when you need to store data between sessions, but can't necessarily use Sessions and Cookies. It's a very extensible way to save data. It's also good for having a standardized output of information from your site (i.e. RSS feeds).
XML can take on a style, and be shown through the browser without HTML, through the use of XSL(T).
Honestly, XML's more than nested arrays; however, they have plenty of similarities.
Those are just my opinions and observations though....