Discernment (distinguishing good from evil v14 or identifying what is Godly and what is not) is something a follower of Christ should do everywhere, all the time. This is not just to be used everywhere in the book of Hebrews but in the whole of scripture and in all of life.
The writer of Hebrews is explaining a spiritual truth in 5:1-10 concerning the fact that Jesus is a high priest designated by God v10.
Then the writer stops and says:
11 About this we have much to say, and it is hard to explain, since
you have become dull of hearing. 12 For though by this time you ought
to be teachers, you need someone to teach you again the basic
principles of the oracles of God. You need milk, not solid food, 13
for everyone who lives on milk is unskilled in the word of
righteousness, since he is a child. 14 But solid food is for the
mature, for those who have their powers of discernment trained by
constant practice to distinguish good from evil.
The point is that the readers have much to learn but have stopped listening - become dull of hearing - and now need to re-learn basic things they should have already learned.
"unskilled" = apeiros, Strongs G552 inexperienced
"word of righteousness" v13
logos dikaiosynē, Strongs G1343
It's not specific to scripture but includes any word of righteousness.
The "constant practice" refers to practicing differentiating what is good from evil not just in Hebrews or in scripture but in all of life.
We know that "only God is good" Mark 10:18 so distinguishing good from evil is knowing what is Godly and what is not.
Constantly seeking what is Godly and what is not would be the constant practice in the passage that makes a follower of Christ skilled or experienced in discernment.
How do we know what is Godly from what is not?
The Holy Spirit
John 16
12 “I still have many things to say to you, but you cannot bear them
now. 13 When the Spirit of truth comes, he will guide you into all the
truth, for he will not speak on his own authority, but whatever he
hears he will speak, and he will declare to you the things that are to
come. 14 He will glorify me, for he will take what is mine and declare
it to you. 15 All that the Father has is mine; therefore I said that
he will take what is mine and declare it to you.
Trustworthy sources and Scripture
2 Timothy 3
14 But as for you, continue in what you have learned and have firmly
believed, knowing from whom you learned it 15 and how from
childhood you have been acquainted with the sacred writings, which are
able to make you wise for salvation through faith in Christ Jesus. 16
All Scripture is breathed out by God and profitable for teaching, for
reproof, for correction, and for training in righteousness, 17 that
the man of God may be complete, equipped for every good work.