Killer Instinct

As with most of these achievements, I recommend Survival as it is endless and you can leave at your leisure

By just fighting, through these, I tend to unlock the 80 Fight Challenges achievements around level 30 as a rough guide. Of course, you can go for specific challenges, but more than enough for this come naturally; I'd see what needs completing after this for the specific "Master" achievements

I make a point to throw at least once per round as this is the challenge I universally make the least progress on

All in all, you will work toward this unknowingly as you work on the character's other specific achievements