I started to use Multisim about 4 years ago. At the beginning I had just an evaluation product, but since 2014 I had the opportunity to use a registed version (I've got the registration from one of my students). I am now using Multisim 13.0 and I am very satisfied with it. 20 years ago, when the electronics simulation software was at the beggining I was using PSpice for my needs of designing IC schematics. I changed to Multisim because it is easier to draw the schematics diagram, the number of (electronic) symbols available is overwhelming, and the simulation is perfect. I am not saying that Pspice is a bad software but when compared with NI Multisim, NI Multisim is like driving a fast new car instead of a 100 years old Ford. What is amazing in Multisim is that you can learn it after 5 minutes of using it. And of course NI Multisim comes with UtilBoard, another software where you can transfer the schematics that you have just made, and have a board designed with ease.
I guess Multisim is still offering the evaluation version, but in this version the number of libraries (and electronic symbols available) is limited. So go with the registered version of the multisim and you will not regret.
When compared with Pspice, it is not so easy in Multisim to edit the simulation MODEL of a device. You have this possibility of course, but in Multisim, each symbol comes with its MODEL pre-defined. You do not have a library of MODELS available and easy to edit and change.