Immutable value types and immutable reference types are semantically all but identical; the only differences are that reference types support reference equality checks that may or may not be meaningful, and that value types may be wrapped in a Nullable(Of T) while reference types are implicitly nullable. If a type is going to be immutable, depending how it will be used, there may be performance reasons to favor a struct or a class; structs are faster for some operations (nearly all operations, for sizes less than four bytes), while classes may bare faster for some others (especially for things larger than 16 bytes). Further, some types of operations are essentially impossible with structs.
Mutable struct types are useful, contrary to what some naysayers claim, but there are some caveats. If one has a variable that holds a reference to a mutable class object, and one does something to change that object, that change will effectively be "seen" by everything that holds a reference to that object. If one wishes to change an object without disturbing anything else, one must know that one holds the only reference to that object. Often times the only way to be sure of this is to copy all the data from the object into a new object instance, and then make the change to that new instance. By contrast, if one has a mutable struct, one can simply make whatever changes one wants without having to create a new instance.
The only real problem with mutable structs is that .net uses various abstractions to make them behave as part of the unified type system, and these abstractions may cause copies of structures to be used in places where the originals logically should be used. It's not always obvious when these substitutions may occur, and they can lead to confusing and erroneous behavior.