My experience of introducing inexperienced programmers and Web developers to TT is that they find its dot notation easier to deal with than Perl's arrows and curly braces. The ambiguity caused by simpler syntax doesn't cause these people as many problems as the simplicity solves.
My experience with trying to explain logic to non-programmers fits yours: I had trouble explaining HTML::Template's TMPL_IF construct to one HTML designer. I think TT's syntax helps some junior programmers, though.
Your preference for using an existing language (Perl) over a mini-language (TT) fits the philosophy of Ruby's Rails project. I don't have a strong preference for either approach, but I think a separate templating system suits me better. As ever, choose the technology that suits not only the problem, but also the people who will solve it.