without using any modules

Without anything but DBI hopefully? Avoiding using that would be a mess.

It's probably not very efficient to do it the way you have in mind, but it might look like this:

for my $r (@values) {
    for my $k (keys %$r) {
        print "$k: $r->{$k}\n";
    }
}
[download]

A better way would be one row at a time:

my $sth = $db->prepare($sql) or die $db->errstr;
$sth->execute or die $db->errstr;
while( my $h = $sth->fetchrow_hashref ) {
    for my $k (keys %$h) { # also see each()
        print "$k: $h->{$k}\n";
    }
}
[download]

## Gen some random test data
my @a = map{ { map{ int rand 100 } 1 .. 10 } } 1 .. 10;

## Print the hashes one per line sorted by key
print "$_\n" for map{ 
    my $href = $_; 
    join ', ', map{ 
        "$_ => $href->{ $_ }" 
    } sort{ 
        $a <=> $b 
    } keys %{ $href } 
} @a;

__OUTPUT__
2 => 28, 36 => 20, 49 => 97, 66 => 26, 72 => 28
25 => 99, 32 => 68, 46 => 70, 98 => 75, 99 => 49
37 => 64, 39 => 55, 43 => 29, 76 => 31, 90 => 48
21 => 33, 22 => 34, 76 => 36, 93 => 78, 96 => 14
31 => 69, 40 => 3, 54 => 20, 64 => 86, 86 => 7
17 => 36, 43 => 21, 53 => 8, 68 => 2, 95 => 69
3 => 12, 73 => 98, 89 => 49, 96 => 41, 98 => 46
9 => 90, 67 => 47, 73 => 22, 83 => 10, 85 => 67
20 => 12, 31 => 23, 36 => 75, 59 => 62, 92 => 28
45 => 21, 64 => 92, 90 => 45, 92 => 60, 93 => 69
[download]

To what end? For debugging, or for presenting a report to the boss? Acceptable output is very different for the two situations.

Perhaps you could provide two or three items of data and indicate how you would like them presented. Even better would be if you were to write a little code as a first attempt at printing the data as you would like to see it, then ask how to solve any specific problems you encounter along the way.

But, I want to print the value @values without using any modules

What for? Homework? How 'bout something like

for my $h (@results) {
    print "{",
      (join ", ",
          map "'$_' => '$h->{$_}'", keys %$h),
      "}\n";
}
[download]

anyway?