On the list of players or coaches, only those who were previously assigned as national team players/coaches will appear. Therefore, before assigning them to the match, they must be marked as national team players/coaches.
To do so:
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Open a player/coach card
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Press the Options button → New registration (National team) button.
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Inspect the National team registration details and hit the 💾 Save button
Once you have done that, the player/coach is marked as a national team player/coach, and it is possible to assign him to the match.
If a player/coach, for any reason, can no longer be part of a national team, they can be deleted in the same way they were added.