use Data::Dumper;

my (@keys, $format, @data, @sizes);

$_ = <DATA>;

while (/\G(\S+)\s+/g) {
    push(@keys, $1);
    push(@sizes, $+[0]-$-[0]);
}

$format = join("", map { "a$_" } @sizes);

while (<DATA>) {

    # if you want a hashref for each line:
    my $i;
    push(@data, { map { ($keys[$i++], $_) } unpack($format, $_) } );

    # else, take out references to @keys above and just use this:
    push(@data, [ unpack($format, $_) ] );
}

print Dumper(\@data);

__DATA__
Name            ID      PS      Gender     Age      Month    Code      Cap        Pool
LName, FName    99999   99      M          99.9     12/2000  Add       99.99      99.99