Yes, you can layer the iron on vinyl.... Make sure the first layer is completely cooled before layering (I'd wait at least 15-20 minutes or more). The second layer takes less pressing time. Here's one I actually did with 3 layers-- black bottom, yellow on top and black on top of that. Once all the layers are ironed on, run an iron quickly over all of the layers, it melts them together (just 5 seconds or so). Different vinyls handle this process differently, so practice first. It is a must that you use parchment paper over the whole design as well.