There is no such thing as star power for rec letters. Adcoms aren't impressed by some kid getting a rec letter from the big boss.
Get letters from people you work with closely and who you believe will spend the most time on them.
Thanks Alex. It sounds like you're steering me towards option 3. However, in the case of option 2, it would still be my current direct supervisor writing the majority of the letter. The only difference is the CEO would be adding some "pizzaz" (as he likes to call it) to it, and then signing off on it.
So in terms of quality of the letter and time spent crafting it, there will be no diff since the same person will be writing most of it; the only difference is the person's signature and title on it. If that's the case, would you still recommend option 3 over option 2? This is only a sticking point for me because friends of mine who had been admitted to top 3 schools in the past have had some pretty high ranking people serve as references.