I've got a light background in statistical analysis for project management, but I've never applied statistics to analyze RPGs or games for that matter at all. I'm looking to compare options within classes as well as options between classes to optimize characters. I know tools like anydice can help me look at the probability statistics for dice, but beyond that I was wondering if there were other resources that could help me, specifically any guides for noobies getting into this sort of thing.
Given that you have a background in statistics, and as an R user myself, I recommend the R statistical programming language. It's completely free, reliable and has a comprehensive library of statistical analysis functions. There is a bit of a learning curve with R, but StackExchange is the right place to be if you have programming questions! :)
Check out this blog post where a Monte Carlo combat analysis of a million fighter class characters was conducted in R.