The 5.56 chamber has a longer lead and it's been beat to death around here. Do a search and you''l find threads on the difference.
As far as accuracy goes, the 223 chamber will be more accurate then the 5.56. The 5.56 will be more reliable if you are going to be firing many rounds of ammo. I have a bushmaster 20 inch ar with the 5.56 chamber and I can get 1 in groups at 100 yards with the stock rifle, with a scope and handloads. This is a chromed lined barrel also.
If you want the most accuarcy out of your rifle, I would go with a match barrel with a 223 chamber. That's in an AR. I reload all of my ammo so I could work the load up so it's safe in my rifle. If you plan on shooting surplus 5.56 ammo, I wouldn't shoot it in the 223 barrel personally but that's your call. Besides, the 5.56 ammo is probility going to be less accuarct then the 223 hunting/match ammo your going to be buying.
Why not let us know what kind of rifle your thinking of getting and what kind of accuracy you are looking for.