You always need your E to actually cancel animations on her, otherwise it'll not work.
Common ones are:
E then immediately click Q > W together, will cancel the Q animation.
E then immediately click W > Q together, will cancel the first W animation.
E then immediately click R > Q together, will cancel the first R animation.
E then immediately click Q > R together, will cancel the Q animation.
Then the flash variations and stuff:
E > Flash > Q > W
R1 > E > Flash > Q > W > R2
etc.
There might be a few more cancel animations, I don't know her exactly for sure. However, the main idea is to always cast E first, and then press 2 of the same buttons together, otherwise you waste too much time and you'll not cancel any animations. Riven's animation cancels all revolves around her E in order to function, if you try to make an animation cancel only using Q + W, then it'll never work.
Common ones are:
E then immediately click Q > W together, will cancel the Q animation.
E then immediately click W > Q together, will cancel the first W animation.
E then immediately click R > Q together, will cancel the first R animation.
E then immediately click Q > R together, will cancel the Q animation.
Then the flash variations and stuff:
E > Flash > Q > W
R1 > E > Flash > Q > W > R2
etc.
There might be a few more cancel animations, I don't know her exactly for sure. However, the main idea is to always cast E first, and then press 2 of the same buttons together, otherwise you waste too much time and you'll not cancel any animations.