This code produces the output you want:

$ perl -Mstrict -Mwarnings -E '
    use List::MoreUtils qw{pairwise}; $a || $b || 1;
    use Data::Dumper;

    my @array = qw( 111 222 333 444 555 888 );
    my @array2 = qw( acct1 acct2 acct3 acct4 acct5 acct8 );

    my $data = [ pairwise { +{ $a => $b } } @array, @array2 ];

    print Dumper $data;
'
$VAR1 = [
          {
            '111' => 'acct1'
          },
          {
            '222' => 'acct2'
          },
          {
            '333' => 'acct3'
          },
          {
            '444' => 'acct4'
          },
          {
            '555' => 'acct5'
          },
          {
            '888' => 'acct8'
          }
        ];
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Notes on my code:

• I've excluded the duplicate acct4 (noted earlier by jeffa).
• See List::MoreUtils for details on pairwise().
• $a || $b || 1; stops "used only once" warnings for both $a and $b. Another way to do this would be with no warnings 'once'; but that's less specific and could potentially mask other, unrelated problems (see perllexwarn).
• The + in front of { $a => $b } indicates to perl that this is a hashref — without it, perl interprets { $a => $b } as an anonymous block.

Notes on your code:

• In scalar context, @some_array evaluates to the number of elements in @some_array, so my $vals_1 = @{$got1}; will result in $vals_1 having a value of 6 (ditto for $vals_2). This would have resulted in messages about trying to use 6 as an array reference. (It would have been better if you had shown your error messages rather than just saying "... having issues ...".)
• The output you say you want ($VAR2 = [ ... ];) is an arrayref; however, your code is populating hashes. Take a look at the Perl Data Structures Cookbook. If the output that you indicated you wanted is not correct, please clarify what you do want.
• In the context of your code, where you use print Dumper %data; you probably want print Dumper \%data; (ditto for print Dumper %hash_of_data;). Take a look at Data::Dumper.