I've installed Monkeytalk on my machine, it has OS X 10.8.5
I had a successfully run an automatized test on Android with Monkeytalk, so I moved on X Code 5.0.2. Created a sample application (iOS 7.0), added the required targets, changed the Schema name too. Also added into Buid Phases the required libraries, mentioned here, as well as the Build Settings' Other Linker Flag option (-all_load). Now, I can successfully build the app to the new Monkey target, appears on the simulator correctly. But after selecting the iOS Simulator in the Monkeytalk IDE, however the console's output is "Connected to Device: iOS Simulator", the record button is not enabled.
I've watched the tutorial video about running Monkeytalk on iOS simulator too, the linker flag mentioned there is -all_load lstdc++ if I understood correctly (the quality of the video wasn't the best and I could not read the line). Did you ever get this problem?
Edit: I've tried to run via networked device, the Monkeytalk is successfully connected to the device, but the record button is still not enabled.
Did you get message in XCode's log output like the last photo of Installing the MonkeyTalk iOS Agent?(Sorry, I don't get the permission to attach images here yet)
If not, make sure you added all the required libraries into Buid Phases and run in CORRECT target first(I met this problem once because of this :<). Then you can check the log output and google these messages for help.