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There are two major classes of natural fabrics: cellulosics like linen, cotton, jute, ramie, etc. They're made of cellulose (cotton is very close to chemically pure cellulose!). and where is cellulose found in plant cells?
Take a look at the chemical structure of cellulose -- it's made of beta-linked glucose chains, rather rigid and not terribly happy about folding. In fact, linen that's pressed hard will start to split on the pressing lines after a few years because of breakage of the cellulose chains.
Animal fibers are protein -- wool, silk, vicuna, camel, etc, so they're amino acid chains. Keratin is kind of globby and tends to wind up back on itself because of cysteine-cysteine bonds, which helps give wool (and curly hair) its characteristic crimp.
Then there are regenerated cellulosics like rayon, tencel and bamboo rayons -- wood pulp has been broken down and delignified by chamical processes, then the cellulose chains are allowed to regenerate. giving fabrics much like cotton. And modified cellulosics like acetate, which is really cellulose acetate -- cellulose that's had acetate groups added to it, which makes a silky fiber that melts easily.
And finally there are the true synthetics, which are long chain polymers of various hydrocarbons. Nylon is a polyamide. Polyester is a terephthalate polymer. Fiber properties here depend on the chemical structure, how fine the fibers are spun, and on shapes of the fibers -- trilobal polyester is an extremely good imitation silk in terms of hand and gloss, though it has much different warmth and absorbance properties, to name just two.
The question you're asking is really a very large one, and it's probably best answered by a basic textiles textbook, of which there are many. I recommend the ones by Saddler, Kaden, Armstrong, and Gioello for starters. Most libraries will have access to one or more good textbooks on the subject.
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