Lightroom cannot create "double exposure" photos.
You could use Photoshop or Photoshop Elements to get close to double exposure photos.
Getting close? What does that mean? Could you please be more specific? What software program do I need exactly? Amazon link?
Have a look at Photoshop or Photoshop Elements.
There are lots of tutorials online for creating double exposures. Google "photoshop double exposure" and you'll find plenty to explore.