All the other characters have a secret compatibility or friendship stat. To get Rikku to throw the ball, kill the person who is throwing it currently and keep healing Rikku (must be with Tidus I think) and you'll get it eventually. A more short term solution is just to do it with the other females dead.
It involves alot of work, but during the game you should remember some points:
1. Whenever characters are dotted around a particular location, talk to Rikku first
2. When Lulu asks you if you fancy Yuna, do not reply that you prefer Lulu.
3. Have Rikku heal tidus or Tidus heal Rikku.
4. If your desperate, get Tidus to kill Yuna and Lulu constantly so their relationship goes down.
This should hopefully work!
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<Thanks Rukie 
< Rukie again
<Again Thanks Rukie 
It's amazing
