I always start characters with the head, because it's the main and the most difficult part of the model. By doing this you can check with your boss or your client if the model is going in the right direction.
I usually use standard poly modeling. In almost every case, I start with a box (or a basic primitive like a cylinder, sphere, etc.). You should move it to X: 0, Y: 0, Z: 0; doing this you can eliminate half of the box, knowing you won't have weld issues when applying the symmetry and turbo smooth modifiers.
In the case of Goofy I tried a different approach, I did a spline on the side view with the few vertexes possible, then I applied a extrude modifier. Then I was able to convert the spline to an editable poly and started tweaking and extruding my edges to get the final shape (Fig.04).
The clothes were done in the traditional way. In the case of the jacket I did just the outside part of it, then I applied a shell modifier to do the inner part. Keeping this modifier alive is a good idea, especially if you're going to "skin" your character (Fig.05 - 06).
I like to set up the basic colors of the scene before texturing. This way you know the mood of your scene before doing the hard job in Photoshop. So I created a color palette for my model and checked it over before applying these flats colors to my model. There are several applications that make color palettes starting with a color of your choice (check out Adobe Kuler for instance). When doing this, I would advise that you have a medium grey background on your renderer.
I used Photoshop for the textures and I did diffuse, bump and specular maps for all the objects in the scene.
I wanted to use mental ray for this render - it's great to have it in Max - so I used mainly the Arch & Design materials. These materials are maybe too heavy to render a complex animation, but they work fine for a single render.
Here you have two examples of the textures and the materials used in the scene (Fig.07 - 08).