You use the Create Index functionality in Management Studio and add both columns. There is a checkbox to define the index of both columns together as being unique. And yes, you can do this along with a standard primary key as you've done here.
If you do not "need" a uniqueidentifier as your primary key (ie a bigint might be a better idea), I would suggest avoiding the use of them. You'll find that your index can become more fragmented more often and it makes the index itself bigger. I have apps that "need" it to be a unique identifier. Just saying that if it isn't truly necessary, use a different data type.