Lightroom automatically chooses its own primary External Editor, based on registry entries on Windows and preference files on Mac. It’ll generally default to the newest version of Photoshop, and if it can’t find Photoshop, it’ll use Photoshop Elements instead. There’s an old TechNote which explains further: http://www.adobe.com/go/kb401629
However, what if you want to use an older version of Photoshop, for example, to use plugins which are unavailable in the latest version? It’s really simple – open that version of Photoshop yourself. If Lightroom sees a Photoshop open, it’ll ignore its own preference, and use the open version instead.