I would agree with you that XML::LibXML is also a good choice. In my (oddly enough limited ;--) experience, it feels a little "lower-level" than XML::Twig, mostly because it forces you to use the DOM to process the data, while XML::Twig has (lots of!) higher-level methods. I agree that it implements very well quite a few standards, and it probably lends to more rigourous code than XML::Twig.
One word to correct you on one point: XML::Twig did not offer real XPath support: it does now, if you use XML::Twig::XPath, which simply re-uses XML::XPath engine.