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The database that you pick will mostly be based on the language that you want to write your site in (php, asp, perl, java, ruby). MySQL and PostgreSQL are both good starting choices because most web technologies/languages openly support both of these. If I had to pick one for a beginner I would pick MySQL. Try using xampp, which has a bundled apache/php/mysql setup that will allow you to use phpmyadmin (a GUI db manager) to do the actual table design.
Alternately you could use an existing content management system that has support for ecommerce, something like Drupal or Joomla.
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