Another solution would be to "standardize" the config file so that each section followed the same format.

[Section2]
user1=pass1:50
user2=pass2:51
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Then simply use Config::IniFiles to tie the file to a hash:

tie my %ini, 'Config::IniFiles', ( -file => "MyConfig.ini" );
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Then to retrieve the data from 'Section2':

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