I'm sure you seen them somewhere, I was wonderin' if anyone knew how to even make them? or if I need anything to MAKE textures other than the template.

Thanks in advanced.

I know of three useful tools for texturing.
GIMP (free)
Photoshop (not free)
Paint.net (free)

GIMP and Paint.net are both quite simple to use... Simple and pretty powerful.
Photoshop is a lot harder to use, but when you know how to deal with it, you will end up making excellent textures.

Spinny head tutorials...
For GIMP
For Photoshop CS4

you may also want to try out http://www.sumopaint.com

its like Flas-o-shop

I have Paint.net, but do I need like..to buy the head textures to sell them?

You can sell heads even if you don't have a Head Texture item.
You can preview them without having the items...
This should help you out.

I'm sorry I'm so nooby. Thank you again..

No need to be ashamed from asking questions. :v
It's perfectly normal. Even the higher ones sometimes ask questions like these.
Just don't worry, okay?