myList.Count is a method on the list object, it just returns the value of a field so is very fast. As it is a small method it is very likely to be inlined by the compiler (or runtime), they may then allow other optimization to be done by the compiler.
myList.Count() is calling an extension method (introduced by LINQ) that loops over all the items in an IEnumerable, so should be a lot slower.
However (In the Microsoft implementation) the Count extension method has a “special case” for Lists that allows it to use the list’s Count property, this means the Count() method is only a little slower than the Count property.
It is unlikely you will be able to tell the difference in speed in most applications.
So if you know you are dealing with a List use the Count property, otherwise if you have a "unknown" IEnumerabl, use the Count() method and let it optimise for you.