The main difference between the two lies in their framework. For Mahout, it's Hadoop MapReduce, and for MLlib, Spark is the framework. Spark MLlib has proven to lack the functionality of Mahout. Evidently, Mahout is built on the top of MapReduce and is mature and includes many ML algorithms for you to choose from.
Learn everything about Mahout by enrolling in Mahout Course and here is a video tutorial which you can watch to learn more about spark:-