No. Experience is not based on peer review. Remember that the majorty of the votes are cast by "low level" users, most of them not having the knowledge of experienced Perl users. I often see postings that only appear to answer the question (but are either wrong, incomplete or answer a different question), get 30 or more reputation points, while a short followup saying "duh, you're wrong, because of <foo>" gets -5 points because it wasn't covered in honey.(Update: this node isn't quite covered in honey, and within a minute, it had accumulated negative points. qed?) Not to mention that the question itself gets a lot of points. I also see off topic questions, FAQs and questions whose answer is found trivially in perlfunc.pod often get voted for; specially if they appear on the front page. I wouldn't be surprised if you could make saint within a few months by just asking questions. OTOH, if you have the most brilliant answers, including many complete programs or modules, but you take a day or two to answer, experience comes in much more slowly. There is some positive correlation between experience and quality of posts. But experience is also influenced by quantity of posts, activity on the site, popularity and time between asking and answering. Just take a look at the best nodes page, featuring nodes with obscure programs, or how to impress women. Nothing wrong with the nodes, but not something I find useful as a reference of Perl mastery.

Assuming people know what they are doing just because they piled up a bunch of experience is pretty naive.

For example, if I were a high level, could I use PM as a reference of sorts with an employer to verify my experience with perl?

You could of course always use PM as a reference, and have the employer (or one of the technical people) read up on you. However, in just a few questions one can get a good impression how well someone knows Perl. Here's a really nice question for a job interview: "How do you think Perl can be improved?", and just let the interviewee talk for a few minutes.

-- Abigail