"I am good at English." Or "I am good in English."
Fluent sounds better. But again...
"I am fluent at English." Or "I am fluent in English."
When referring to a school subject we do say at
I am good at Geography
so you could say
I am good at English
If you are describing your capabilities in the language then fluent is probably better and then use in.
I am fluent in English, Spanish and German
We may well phrase it differently, when emphasising some particular aspect of language skills
I speak English fluently