Well, thats the art part =)
Learning a sense for proportion and to know anatomy, at leat for realistic organic models like humans, animals and stuff like that, for stylized characters like e.g. Pixar does it doesn´t matter that much, but I guess that is not what you are after.
I recommend to get some art and anatomy books, or just work by reference for particular characters.
3d.sk offers some great free resources many used to start organic modeling.
Else I´d start here and familiarize myself with the basics, like Head to torso ration, leg to head ratio, shoulder to hip ratios and how they influence the appearence, differences is male and female skeleton and proportions.
http://tinyurl.com/3xa7n9n
It is a tough area of expertise to start out with, many consider realistic human modeling the ultimate challenge
But you can use the forum search for topology and proportion, and look everywhere, that basic knowledge is not limited to blender or 3d software, it is a basis of many arts, from pencil drawning over sculptors, painters, stonemasons, tailors and many more.
I occasionally landed on pages and papers for plastic surgery during my organic modelling research phase =)
Also a nice resource is to look into PHI, the golden ratio =)
And always keep in mind, in realistic organic modeling you hunt to capture the imperfection of organic matter. Perfect organic stuff looks artificial…