If your set up is a simple toolbar-as-pane-switcher deal (a la Apple Mail's preferences window), all you need to do is implement -toolbarSelectableItemIdentifiers: to return the same as -toolbarDefaultItemIdentifiers: and -toolbarAllowedItemIdentifiers:. NSToolbar will then automatically highlight items when they're clicked.
If your setup is more sophisticated -- say, like System Preferences where you can select a pane without clicking it on the toolbar -- you'll still need to do the above, and then call -setSelectedItemIdentifier: whenever you want the selection highlight to change.