Which one is correct as a headline: "for all Polish learners" or "to all Polish learners"?

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The answer to this question depends on what you are trying to say.

If something is "for" someone, that means that it was written in order to benefit them.

If something is "to" someone, it means that the statement is directed at them.

So for example
"This was written for all Polish learners"
Would mean that Polish learners are the people you are writing to help. You are saying that what you wrote would serve some kind of purpose for them.

But
"This was written to all Polish learners"
Would mean that Polish learners are the ones being addressed. They are the people who you think are going to be reading it.

Neither of these phrases could stand alone as a headline, because there isn't enough information in them. Depending on what exactly you are sharing "to" or "for" all Polish learners, you would need different headlines. Here are a few examples.

Helpful tips for all Polish learners.
Charts for all Polish learners.
Vocabulary words for all Polish Learners

An open letter to all Polish learners.
Show this to all Polish learners.