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for best results illustrator will give you better edges however photoshop cs6 has great improvement on vector art than previous versions.

for ease of use I would choose photoshop it is easier to get to grips with and you have the added bonus of exporting it as an illustrator file if that is what is needed for print.

Honestly though if your budget allows you to then I would go for both I often program hop between the 2 when doing things I am sure everything I hop to a different program for is available in both but I guess if you know how to do something easily in 1 I choose to do that.