"Nem" and "não" can be used as synonymous in many sentences, but there is a thin difference between them, "nem" would be translated better as "not even". Example:
Ela queria que eu lhe telefonasse, mas nem tinha seu número.
She wanted me to call her, but I did not even have her number.
Furthermore, "nem" can be used as an additive conjuntion in negative sentences, presenting a non-contrasting negative idea, like English "or/nor" while "não" is always an adverb.
Não gosto de leite, nem de café.
I don't like milk nor coffee.
Besides, only "nem" means neither (or either in negative sentences)
Não gosto nem de café, nem de leite.
I don't like either coffee or milk.
Tu não gostas de café?! Nem eu!
Don't you like coffee?! Neither do I!
When answering a question, you have to use "não".
- Tu gostas dela?
- Não, não gosto.
- Do you like her?
- No, I don't.
"Não" can also be an interjection:
Não! Volta aqui!
No! Come back here!
I think that's it... I'll write another sentence to show you the little difference:
Eu nem vou à festa...
I'm not even going to the party...
Eu não vou à festa.
I'm not going to the party.