I'm running Mac OSX Mavericks (10.9) w/ the latest Xcode (5.0.2) and command line tools installed.
Which, if any, version of OpenCV is the best bet for avoiding build and/or compile errors?
I think you should go with the current release 2.4.7. The sources can be downloaded from the official opencv page. On OSX, you can use also MacPorts to install precompiled OpenCV libraries as described here.
Personally, I build OpenCV without installing it to the system libraries. Instead, I'm pointing in my project just to the OpenCV build directory. That's very easy with cmake.