iOS 6
In my preliminary testing via the simulator, checking the application state with
[[UIApplication sharedApplication] applicationState]
in either
- (void)applicationWillEnterForeground:(UIApplication *)application
- (void)applicationDidEnterBackground:(UIApplication *)application
allows you to differentiate between a call to lock the device and just switching back to the homescreen. A lock screen will return 1 (UIApplicationStateInactive), whereas a home button press will register as a 2 (UIApplicationStateBackground).
It seems consistent and should work on an iOS device just as reliably as it does in the simulator.
iOS 7
The iOS 6 method no longer works in iOS 7. In order to do this now, you have to utilize CFNotificationCenter and listen for a darwin notification (labeled: com.apple.springboard.lockcomplete). You can find the github repo with the sample project here: https://github.com/binarydev/ios-home-vs-lock-button
Credit for the iOS 7 fix goes out to wqq