Once you install Web Quest Surfer, it will be preloaded with a set of categories and will open up on the Welcome category. In the Welcome category you will see my website on one tab and the help for the app on the second tab.
The upper left popup button has the list of most recently visited categories, so initially, you will need to click the globe icon just to the right and select the category tree view (Palm Tree icon). Then you can click on some of the pre-defined categories. Good Examples are the General category underneath Books, and the DVD category underneath Movies (as seen in the screenshots in the Mac App Store for my app). From these categories, you can type in something to search for at the top or right click on something in one of the tabs and tell it to search all sites in the category.
Websites may be either set up with static URLs or searchable URLs, so only the searchable sites will kick off a search when you tell it to look for something.