Hello!
Mary's answer is very good.
"Afuera" means outside, outdoors. ( "vamos afuera a hablar" = "let's go outside to talk " )
You can also use it to say: "get out of here!" = " fuera de aquí!"
In many occasions it's possible to use indistinctly one word or another.
But the local determination (place, location) is more precise in "fuera". Means outside a place or definite limit. "Afuera" indicates the general idea of distance (inside / outside) and can have grades (more, less, much, so out).
Maybe these examples help you to understand the difference.
" Ana está afuera." = Ana is outside.
" Ana está fuera de la casa." = Ana is outside the house.
I hope to have helped.
Sofía.