Purchase a partially sand-based concrete rather than one that is solely rock-based. Sand is finer and contributes to a smoother pour and cast.
Add a fine aggregate to regular rock concrete. In most cases this is simply a sandy material that can be manually added to concrete and purchased at the same location.
Pour the concrete into a pre-made cast or mold. These are available for purchase and allow you to create smooth and sculpted cement blocks and planks before setting them in place. Drying time will take several days or perhaps close to a week.
Take a trowel to any rough concrete and smooth out the edges. This is the most basic approach to smoothing concrete and yet often the most effective.
Smooth over the edges of preexisting concrete by adding a new layer of finer cement. Cover the old cement with a small amount of new concrete to hide the imperfections.