I've noticed both Keil uVision 4 and uVision 5 share the (for Windows) identical filename "UV4.exe"/"Uv4.exe". This results in Windows (7) Explorer being unable to choose for a specific version.
You have to rename the "UV4.exe" from uVision 5 to "UV5.EXE" and update the startmenu shortcut.
The system path decides in which order the system looks for executable programs.
But even if the two exe files would have had different names (and remember that it's possible to rename or make copies of exe files) there is still an issue involved with associating file extensions with a program, when both uv4 and uv5 has project files with the same extension.