When you're starting with Visual C++, you can use this book as a tutorial by going through it sequentially. Later you can use it as a reference by looking up topics in the table of contents or in the index. Because of the tight interrelationships among many application framework elements, it wasn't possible to cleanly isolate each concept in its own chapter, so the book really isn't an encyclopedia. When you use this book, you'll definitely want to keep the online help available for looking up classes and member functions.
If you're experienced with the Win16 version of Visual C++, scan Part I for an overview of new features. Then skip the first three chapters of Part II, but read Chapters 6 through 12, which cover elements specific to Win32.