Clicking the star on the Navigation toolbar will bookmark the page in the "Unsorted Bookmarks" folder and the star turns blue to show that. You can't see bookmarks in the "Unsorted" folder in the Bookmarks menu although there is an Unsorted Bookmarks link at the bottom of the list, so to see them in the bookmarks menu you will have to move them to the Bookmarks Menu folder or the Bookmarks Toolbar folder.

   Clicking the star on the Navigation toolbar will bookmark the page in the "Unsorted Bookmarks" folder and the star turns blue to show that
   Bookmarks > "Bookmark This Page" (Ctrl+D) will bookmark the page in the Bookmarks Menu folder (you need to confirm that)
   "Bookmark This Page" can be accessed via the right-click context menu in the browsing area or via the Bookmarks menu in the Firefox menu button drop down or menu bar (Alt+B)
   If the URL in the Navigation toolbar is bookmarked and the star is highlighted blue then click this highlighted star or use "Edit This Bookmark" (Ctrl+D) in the menu to edit the properties of the bookmark like name and location and move the bookmark to another folder or remove the bookmark 

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Click the bookmarks star once to save the entry into the Unsorted Bookmarks folder. Press the star a second time, and a window will pop up letting you remove or edit the bookmark information.

On the Folder line, press the arrow on the far right to see the whole tree.