First View
When you open Expression web, you may see a view of a blank page. And blank is good to begin with,( but if you are starting a site, you should close this blank page or create a page that can be used later). Microsoft will call it "WorkSpace" like another software "Eclipse" or Adobe software. As a most common practice a web site is created a master webpage like default.asp, index.asp, index.aspx or index.php, so that your web site opens with all the menus and items you want the viewers to browse.
However to get around you may jump to Task Panes, by pressing "alt & k " keys together or simply clicking with your mouse. You must know that the letter with underline is an "action key" meaning with alt and a key will give you quick access of that menu using your key pad. This is life-saving and makes faster to access to the menus.

Further, you like to use the tools like Tool Box, to keep it ready as you create your web pages,

 
As I feel to use layer tool or div tag most often over iframe, I would keep handy on my write. If you have ever used vml or shape tools in frontpage, you don't have call out boxes or shape with drawing tools.