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my %h;

...
for my $k (keys(%h)) {
   print("$k: ", join(', ', @{ $h{$k} }), "\n");
}

kate
dan
...
doug.smith
test
^Z

print "Enter names of user to add:\n";
chomp( my @users = map lc, <> );
...
fore my $i (0..$#users) {
   $adds{$users[$i]} = qx(ls /home/$exusers[$i]/.bash_profile);
}

kate doug.smith
dan test
^Z

my %adds;
print "Enter new user and mirrored user pairs:\n";
...
   my ($user, $exuser) = map lc, split;
   $adds{$user} = qx(ls /home/$exuser/.bash_profile);
}