At work I have coded one project using XML and Perl. Here is what I have learned in doing so:
Rather than using XML::Parser directly, I used the XML::Dom application from CPAN. The DOM is a standard way of interfacing with XML; if you solve an XML problem using DOM then you will be able to port the logic to other languages.
The DOM is tedious to use, and code using the DOM is hard to maintain. Our own Mirod here at Perlmonks is rather an expert on Perl/XML. He recommends his own XML::Twig module instead.
Some databases such as newer versions of Microsoft SQL Server have built-in XML support. They can return a query's results as XML. Use one of these if you can.
Although I plan to use Perl for XML programming again, I now know that Java has more tools for programming XML than does Perl. In other words, Perl may not be the tool of choice for programming XML in every case.