Well, the man pages for Template.pm include a nicely written tutorial section, so I'd really suggest looking at them.

If you installed it in the default place, the pod file will be in /usr/lib/perl5/site_perl/5.x.x/Template.pod. Run that through pod2html and you can have a nicely formatted copy locally.

Also there is a decent and interesting white paper on the template-toolkit website.

Hope that helps,

caleb