In version 5.0.2 of XCode, the best way to accomplish this is probably to add it to the target’s “Search Paths” pane. Locating this was (for me) incredibly unintuitive. Here’s how I got to it, for those as confused as I:
In the left column, click on the Project Navigator icon (looks like a folder). Then, click on the project entry. This should show a bunch of settings in the main pane. At the top of this pane, click on “Build Settings. This shows a bunch of entries… including one called Search Paths… but you can’t add a search path here! This made me gnash my teeth for quite a while, until I figured out that the name of the project at the top of this pane was a pull-down; choose the target from this pull-down, and you should now be able to double click on “Header Search Paths” and perform the needed edit.
Oh, the joy of crazy GUIs.