[Section2]
user1=pass1:50
user2=pass2:51

##</code><code>##

tie my %ini, 'Config::IniFiles', ( -file => "MyConfig.ini" );

##</code><code>##

foreach $user (keys %{$ini{'Section2'}}) {
    ($pass, $uid) = split /:/, $ini{'accounts'}{$user};
    #do something with the values here
}