My general advice is to pick songs that:
1) You know really well 2)That consistently provide a visceral reaction (goosebumps, adrenaline rush or an out of body experience, etc). 3) Has an aspect that you think your current speakers don't handle well (piano, female vocals, drums and/or cymbals, etc).
A few songs that meet some of the above criteria for me are:
DADA: "Dorina"
DIXIE DREGS: "Ice Cakes"
EMMYLOU HARRIS & LINDA RONSTADT: "Sweetspot"
VICTOR KRAUSE: "Shine On You Crazy Diamond"
PREFAB SPROUT: "Faron Young"
STRANGLERS: "European Female"