Time to bring out my hat and glasses.
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Ok, listen my fellow disciples:
The most important thing is edgeflow and edgeloops. Edgeloops are, as the link tZork provided loops around the eyes, and mouth. The mouth can have stretched loops around the nose too. However these are tremendously important if you want to animate the thing you model out. Sure, you can animate things that doesn't have edgeloops and nice edgeflow but you won't get nearly as good results and you will have a much harder time to animate it.
Then to make your edgeflow flow the same as muscles would on the real body, with other words, try to simulate the muscles with the edges. You'll have a much easier time modeling out definitions too if you do that.
Now, there's basically two ways of going about doing this. One way is just to take a sphere/box etc. (a simple shape) and start sculpt it.
Now you can just start practicing to get the anatomy and proportions right if you need that, but the thing is, you don't need to worry that much about the edgeflow. Why?
Because later, when you feel you are done with the model you can re-topologize (I don't know how that works in Blender as I use ZBrush, but it should basically be the same thing, although probably a little different technique).
Re-topologization means that you will lay out the edgeloops on your own directly on the model, then taking that new model and save it (at least in ZBrush), efficiently applying the new egdeloops.
The second way is to build a base model, low-poly, with the correct egdeloops and muscle edgeflow, then divide it to get more detail and start sculpting in whatever you want.
So you would start from scratch, building polygon by polygon and slowly getting the shape of the face with the correct (hopefully) edgeloops already in place. If you're used to this kind of thing you can quickly get a base face/head and start dividing that.
But do keep in mind that building a head or a face is a process without instant gratification, you will need to work on it as it probably won't look too good at first. Also, creating correct and really good edgeloops isn't as easy as it might look.
Those are the two most common ways to do it. Whatever you feel most comfortable with and works best for you.
I tend to switch between these methods as I don't really have a preference. However, I do like to lay out my edgeloops before getting into detailing anything. Feels cleaner that way and I don't have to have that sneaky feeling in the back of my head knowing that this is a disaster edgeloop-wise. It throws off my concentration, and nerves.
Research edgeloops on google to get an idea what the hell I was talking about, if you do not know already.
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Ok my fellow disciples. Class over. Go have sex .... or just stay at home, eat chips and drink cola, get fat and watch porn ... or something. You earned it.