After switching to XCode5 I've just re-done all my icons and launch images for an app, with the exception of retina launch images I should have a complete set for both iPad and iPhone, iOS6 and iOS7, thanks to this tool: http://www.appiconsizes.com/
But XCode5 absolutely refuses to use them all. I removed all the old images from my project and added the new ones. Some, XCode automatically detects, seemingly at random. Many others, it says it can't find the images needed even though they are named according to Apple's guidelines (as far as I can see, it's all a bit confusing with so many variants). It lets me find them manually but doesn't seem to be using them properly.
And my launch images, it insists on using images from a different target even though these are definitely not marked to be included in this target. It won't even let me change those ones, if I try to then it just ignores my selection.
A few screenshots follow. I originally had just an "Icon" icon identifier in my plist, since Apple say it will automatically detect different variants, but XCode has then added Icon-76 and Icon-120, seemingly contradicting this. I'm aware XCode5 supports controlling things more through your plist than XCode4, but shouldn't require that - you should be able to tell it the icon base name or use "default" and it would figure things out?