This is easy. If you right click on the start menu and select "explore" it should always open to the user profile to which you are logged in. You will have a folder in there called "start menu". Anything you place within the start menu folder will also show up at the highest level when you hit the start menu button.
For instance the user profile for my start menu is located C:\documents and settings\axxmasterr\Start Menu\
So I wanted to create a folder that contains all of the shortcuts to my security tools. So I created a directory in "Start Menu" called "Security Tools". Within the security tools directory I place all of the shortcuts I would like to have available. If you want to have a particular program be available at the highest level of the start menu, simply place the shortcut into the "Start Menu" directory and it should be right there when you click on the start menu.