Best songs for speaker setup / positioning

You want to start with them at least 3' from the wall behind and at least 1' off the side wall. I always toed mine at least 6" in with tweeter on the inside. The exact spacing will depend on your listening location. I always used something well recorded like jazz or d2d. If you have someone else who can move the speakers while you listen it makes it easier. I always kept a note page with the measurements of the 3 speaker points from the wall with notes on the sound so I would have something to fall back on.
Good luck

Right, the two best are both by Stanley: Tape Measure, and Framing Square. When the speakers are precisely equidistant and symmetrical your imaging will be fantastic. Then experiment with toe to get your preferred balance of imaging, stage width, and tone.  

Then if you still want a track to show off your impressive work get the XLO Test CD and play the track where Roger Skoff talks and walks around the room. When he goes behind you and it really does sound like he has to be back there somewhere then you know you nailed it.

Toe and caster (neg or pos) are the last things to set, just like MC said.

I have a couple of test CDs and  three types of measuring software.
You need none of it once you measure the speakers, your working with.
in the room your working with.. YES it makes a difference.. 

KNOW your room, know EACH speaker (they are not the same.)
Get a measuring tape (laser is cool too), a framing square and speaker test software.

Test to make sure the two speakers are matched first. Within 5% is still 5% better than most speakers if they are checked at all. A LOT of speaker XOs are that far off.. 10-20K speakers are not uncommon, to be 10% different between left to right. AND lows, mids and highs, ARE not averaged... you have to do some inductor tuning...by trimming the lengths.. Mids more so than any...

Correctly tuned OX do not look the same, because of the driver differences. If they look the same they are NOT matched...speakers.
I watched a guy tune a pair one night 22 years ago. A friggin genius.
What a difference, the next week, they were at CES show. There is a left there is a right, and there was an option on the bass section orientation, long room, short room, tall ceiling, short ceiling.

BUT if you insist on NOT doing it right from the start. You have to use the whole CD because it accounts for some the screw ups in the mismatched speakers to begin with. OK. That is what the WHOLE CD, or at least the two or three I have do. OLD SCHOOL ok... Just old hat....

My CD don't account for differences between low mids and highs..

The way I was taught DOES...oh CD optional... But you gotta have some tools. and SPL meter is still a GREAT tool...To learn YOUR room...

Regards