There is no one correct workflow. It all depends on whenther you will be using a Dynamic (Data Base Driven) catalog, or a static catalog.
If you are using a Dynamic catalog, the first thing is to create the database and populate it with your products.
you can either enter the information directly to the database using PHPMyAdmin or another MySQL GUI Tool like [url=http://www.heidisql.com/]HeidiSQL[url] or Sequel Pro
or you can create backend administration pages for your site using DataAssist.
Once you have the database populated, you need to create the catalog pages to display the items.
normally a catalog would start with a search and results page, the results page would link to a product detail page, on the product detail page, you would add the eCart add to cart button.
You can create these pages manually in Dreamweaver, the type of pages you would be creating are referred to as a master detail page set:
Or you can use DataAssist to create the pages for you.