Presumably this is split phase, so the neutrals do not count as a CCC. This you have 4 CCC requiring an 80% adjustment. You must use the 75 temp ampacity due to terminal limitations, but can derate from the 90 degree. It works out using the next size up rule as you have shown as long as you use the 250 MCM, the 4/0 is too small.
Not sure if a 2 1/2 LB is sufficient. You would have to see what it is marked with and of course it won't have the combination of conductors you have. I think there is a letter from an lb manufacturer floating out there that says for combinations not printed on the lb you can compute the area of your conductors and as long as it is the same or less you're okay.