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Usually we choose the correct form by instinct.

For example;-

I am a teacher. (not me)

Give that to me. (not I)

There are other times when people make mistakes with these two pronouns. I/me is difficult when it is coupled with another pronoun or with a noun. This is when you have to think about the subject/object in a sentence.

We use I as the subject of the sentence, but the object of the sentence is me.

For example;-

"I gave the students their homework."

"The students gave me their homework to be marked."

"I marked their homework."

But...
The teacher gave the homework to my friend and me. (Not I)

!If you don't understand why the above sentence is correct, simplify the sentence again.

Deal with the two people separately.

The teacher gave the homework to my friend.
+
The teacher gave the homework to me.

= The teacher gave the homework to my friend and me.

My friend and I gave the homework back to the teacher. (Not me)
My friend gave the homework back to the teacher.
I gave the homework back to the teacher.
= My friend and I gave the homework back to the teacher.

However, when answering questions, it can be a bit more confusing.

Q - Who gave the students their homework?
A - "I did."
or
A - "It was me."
or simply
"Me."
!Note - It is polite to mention other people before you mention yourself, which is whay we say "My friend and I."