@hypersex
My Raspibolt runs the same OS version. I'd assume that you followed the Raspibolt setup instructions and didn't mess up something. If you deviated from the instructions or made other changes that nobody here can know, I'd say: start over and don't mess things up.
What happens and is shown when you execute Core with an absolute path? Like this:
$ /usr/local/bin/bitcoind
Please, show the output of
ls -laF /usr/local/binadmin@raspibolt:~ $ ls -laF /usr/local/bin
total 89088
drwxr-xr-x 2 root root 4096 Jun 3 2023 ./
drwxr-xr-x 10 root root 4096 Apr 4 2022 ../
-rwxr-xr-x 1 root root 2080792 Jun 3 2023 bitcoin-cli*
-rwxr-xr-x 1 root root 38962464 Jun 3 2023 bitcoin-qt*
-rwxr-xr-x 1 root root 3743816 Jun 3 2023 bitcoin-tx*
-rwxr-xr-x 1 root root 1900120 Jun 3 2023 bitcoin-util*
-rwxr-xr-x 1 root root 8602152 Jun 3 2023 bitcoin-wallet*
-rwxr-xr-x 1 root root 13731856 Jun 3 2023 bitcoind*
-rwxr-xr-x 1 root root 22179600 Jun 3 2023 test_bitcoin*
admin@raspibolt:~ $
My executables file sizes will differ from yours as I haven't updated my Raspibolt's Bitcoin Core v25.0 yet. That shouldn't matter for you, I'm looking for other clues why you can't execute the files.
Just to get everything together: your executables are owned by user pi. Your files are world readable and executable, so trying to run them with another user account shouldn't matter, unless this user account has some weird restrictions. Did you tinker with some advanced settings like AppArmor or SELinux e.g.?