Yep, Peter is right. Any structure is a value type, and by definition, always has a value (you will never get a NullReferenceException by referencing a value type variable in code...). Reference types are classes, and the variable only stores a reference to the object, not the actual object, so the reference can be a null pointer (allowing you to get a NullReferenceException). So, Peter is right: simple types are all value types, while classes are all reference types. You can always tell by opening the Object Browser in VS (View -> Object Browser) and looking at the icon next to the type.
You will notice that the symbol next to the IntXX types indicates a simple type, which is always a value type. Also, the symbol next to IntPtr is thicker, which represents a structure, which is also a value type. The thinner symbol next to the exception types indicates that the types are classes, which are reference types.
You'll also notice that when you expand the plus sign beside the value types, they all inherit from System.ValueType. You cannot directly inherit from ValueType (I don't think...), but the compiler automatically does this when you define something as a structure (the same way a class you define automatically inherits from System.Object).
Hope that helps explain things some more