This looks to me like a good opportunity to use a hash slice.

use strict;
use warnings;

my %user_info;

my @fields = qw(name email foo bar);

while (<DATA>) {
    chomp;
    my ($user, $attribs) = split /\s+/, $_, 2;

    my %record;
    @record{@fields} =  split /\|/, $attribs;

    $user_info{$user} = \%record;
}

foreach my $user (keys %user_info) {
    print "Username:$user Real Name:$user_info{$user}{name}\n";
}
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