Does the order of keywords matter in a page title?

Yes, putting important keywords closer to the beginning of a title does help SEO. SEOmoz's ranking factors survey agrees, as do other sources.

Keyword Use Anywhere in the Title Tag
66% very high importance

Keyword Use as the First Word(s) of the Title Tag
63% high importance

Keyword Use in the Root Domain Name
60% high importance

Keyword Use Anywhere in the H1 Headline Tag
49% moderate importance

Side rant: Personally I hate this because it actually devalues user experience in many cases. For home pages, if you are a company selling red widgets a spammy title like "red widgets, widgets, blue widgets" can be more successful that "Awesome WidCo plc - suppliers of red widgets".

I believe the site name should come first on the home page, but SEO forces you to do the opposite.