having it swept really isnt relevent to the question at all other than its associated with stove maintainance
the fire cement goes hard – i have it in my joints that are not very thick – ie same od into same od.
the advantage of the jointing compound is it doesnt set so can accomodate for movement a bit better and may be more resiliant in your application.
either way neither are fit and forget.
as for straightening up the flue – you might find that the hole in the fireplace and the flue registerplate are not alligned. I was told id have to live with a slightly askew pipe or have my stove offset in the hole as no combination of the availible flue pipes would work to get it all centered. Its amaizing what you can do with a grinder and a welder to make your own angle 😉