We will be switching our shopping cart platform from volusion to magento and really cautious / nervous about our rankings / seo stuff. any advice for anyone that has migrated stores, etc. these urls are years old, etc.
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shopping cart platform switch and SEO. What do you suggest? What's the best way to ensure we keep rankings.
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In December 2008 I helped a company transition from BV4 to Volusion. Like your situation, our URLs were years old at that point (the original Website launched in 1996).
I really only have 2 pieces of advice:
1. Make sure you've set up your 301 redirects properly (we didn't, and it took 6 weeks to sort out the mess).
2. Hang on for the ride.
Be prepared for a major dip in traffic, particularly if you are re-writing all of the URLs. But take heart. Sometimes the dip is necessary to move onward and upward. Seth Godin wrote a whole book on The Dip. Now might be a good time to buy your CEO a copy.

Cheers! I hope all goes well and that it moves you one step closer to awesomeness!
Dana