Good question! I suspect we will get a wide range of answers on this. So, I'll start the ball rolling.
The answer hinges on what you mean by "get right to work with it." If you are going to do a glue up or fasten the pieces together mechanically the same day, I would say go for it. If, however, you plan to leave it around for a day or more and get back to it, its best to mill it close to spec, then do the final milling and squaring just before assembly.
When you mill rough lumber, at whatever MC, you will have interior wood at a higher MC than exterior and it will want to stretch and compress as it dries. If you fasten it quickly, the last bits of movement will be restrained. If you just sticker it or stack it, it will bow, twist, etc.
In practice, I usually mill it close to spec - about 1/16, sticker it, then do the final milling just before joinery and assembly.
Of course, it all depends on what your project is, the wood species, the humidity relative to the wood, etc, etc...