Because you picked your PSN account as your main you only get to use those characters in cross safe on all linked platforms.
All other save data on other platform's accounts become dormant.
If you want to use your PC characters again you need to deactivate cross save. If you want those characters on your PS5 then you will have to wait out the 90 day cooldown period and reactivate cross save with your Steam account as your main.
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Might not be explained this well… I didn’t pick my psn characters as my main - my steam characters are listed as my main on the cross save site. I can also play my main characters on steam with no issue. The only problem is when I log into ps5 it says “cross save enabled” on the character select screen with the correct screen name and 4 digit code next to it, but the characters are still my old ps characters, not my mains. Not sure what else to do, don’t really want to deactivate and wait 90 days since I don’t know what went wrong the first time.