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To obtain different paint colors: beat the goal time for one of the following tracks in Time Trial mode.
A different color will be unlocked depending on if you finish in first, second or third place.
Lightning McQueen Figure 8 track
Mater Desert Canyon Dash track
Sally Carrera Radiator Springs track
Wingo Interstate track

Here are some other unlockables.
Boost Defeat Boost during story mode.
Chick Defeat Chick during story mode.
DJ Defeat DJ during story mode.
Doc Hudson With the Gran Prix Cup 1
Sheriff Win the Gran Prix Cup 2.
Snot Rod Defeat Snot Rod during story mode.
Wingo Defeat Wingo during story mode.

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