I own and manage Perl Training Australia. I've been teaching Perl for about eight years, and computer science for over a decade. I have strong opinions on not only Perl, but also on teaching, and presenting in general. I've written hundreds of pages of text about Perl -- which I won't be repeating here -- so what I'm going to give you isn't advice on teaching Perl; it's meta-advice instead.
Firstly, if your time and budget allows, consider sending your staff member on a professional Perl training course. Dedicated courses have the advantage that they don't come with work interruptions, they don't come with workplace politics, and they do come with someone who's very familiar with the difficulties people have when learning Perl. Please make sure you have a trainer who knows their stuff and is an active member of the Perl community; it means they should be able to answer any question thrown at them, or direct the questioner to an appropriate reference where they can learn more. Yes, I run a Perl training business, so I'm heavily opinionated here.
If for whatever reason you can't go with a dedicated course, then get a book that's specifically designed to teach people how to program in Perl, and walk through that. It's easy to miss things, or to try and introduce things in the wrong order, or (heaven forbid) teach bad habits, and all of those can make your life difficult. Often the people writing books designed to teach Perl are the same people who have successful Perl training businesses. If you want to buy a book, I'd recommend the latest version of Learning Perl. If you want to download a book, I'd recommend grabbing the Programming Perl course notes from the Perl Training Australia website.
Both of these books come with exercises, and this brings me to my last piece of meta-advice. Make sure anyone who is learning Perl does the exercises. It's very easy when learning any new skill to think you know what's going on, but discover that when putting things into practice it's harder than it looks. This is particularly the case with Perl, where programming concepts like "context" can apply, which are rare in other languages. Usually the exercises are specifically designed to teach a certain skill, or to highlight a certain pitfall; figuring these things out during learning is much easier than figuring them out on the eve of a project deadline.