Grab an ohm meter, you will likely find that both rails are actually terminated in the exact same place,
also depending on the ATX spec the 3.3V rail is now commonly the regulated one, with a separate sense line joined at the 24 pin socket, so try loading that,
The other thing to be aware of is that with most cheap supplies, if you add up all the channel ratings it will exceed the supply rating, what its actually rated for is the current on the 3.3V rail and the rest share the remaining power capacity,