For something a bit more in depth, I would actually recommend XML::LibXML over XML::DOM. XML::LibXML is actively maintained and is lightning fast. XML::DOM got somewhat neglected by Enno until TJ Mather rescued it last year and put out a release.

Personally I use XML::LibXML both for it's speed (based on libxml2 instead of expat) and because it validates XML against DTDs nicely.

Oh, did I mention how fast XML::LibXML is?