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