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I haven't actually tried it myself, but now that I've read all these posts, I'm curious. Maybe, if I'm just as unsuccessful I can join your ranks and gripe about it.
So I tried to chain fish, successfully reeled in a chain of 120-something (I checked with the fisherman in route 16's shack) and didn't find a shiny at all :'( Apparently there's a lot of emphasis on location too, that some spots have a higher yield for shinies, so that could be important to keep in mind...
I've gotten two shinies from fishing, at 9 reels and 7 reels. Guess I was just lucky. I've gotten to 40-50 loads of times and never had anything to show for it.
I always try to fish in a spot that is surrounded on 3 sides by rocks. I've heard that it further increases the chance of getting a hook... but there may be some correlation between shiny rates as well.