Python's a great skill to learn - I use it for everything. It's the glue language for virtually every tool out there (you can even use it with .Net).
Documentation for Python + LibreOffice is however a bit sketchy currently, although I don't have much experience with Calc.
There is some work-in-progress documentation at http://documenthacker.wordpress.com (or soon www.documenthacker.com). It has examples for working with Writer, rather than Calc, but you might still find it useful.