Hey Dan,
I would go with website.com/main-category/product-name - its structured more logically.
SEO wise I don't think it will make much difference.
you would think it would be better as website.com/product-name/main-category
because people would search for: "nokia 6230 mobile phone" and that setup would mean your site structured like so website.com/nokia-6230/mobile-phones and it's a better match for the search term.
My testing has been non-conclusive.
Just make sure your page title reads "product name main-category" such as "nokia 6230 mobile phones" and the SEs will like it.
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