Here's how to add a command to one of the toolbars in Visual Studio (or how I know how to do it, anyway):
1.) Click the little down arrow at the end of the toolbar, select "Add or Remove Buttons", then select "Customize..."
2.) Now click the "Add Command..." button on the right.
3.) Click "Edit" in the left scroll list and then scroll down on the right until you see the two "Outline Toggle" commands:
4.) Choose one (I'll choose "Outline Toggle All" to toggle outlining in the entire open document) and click "OK."
5.) Now that command will be apart of the toolbar who you first clicked "Add/Remove Buttons" to. You can re-order the command to put it in different positions in the toolbar. Here's an example where I've added it to the main toolbar that has your typical Save/Undo/Debug commands: