Since VS is sharing HTML designer with Expression Web, many videos available for Expression Web may also be useful for Visual Studio users.

LearnExpression is a great site with many videos on designer tools and page layout: http://www.learnexpression.com/. There are also videos at the Microsoft Expression sites here: http://expression.microsoft.com/en-us/cc197140.aspx

Use CSS Layout in Expression Web

Sophisticated CSS-based Layout and Formatting

User CSS Style Sheets in Expression Web