In my Wifes 2015 Tahoe Flex fuel What I have learned is E85 is not good in a sitting tank or system. It will condensate quickly and then will rust a sitting system. We run it if the tahoe is always being used. The overnight and cold weather start ups and the smell you get is the condensate cleaning out your system. Most throttle and injector cleaners are 80% water. And yes e85 does run cleaner than most 87 and 91 octane fuels.
The sad truth about those octanes is they are actually a blend of things, that blend is constantly being changed in the USA, especially from summer to winter, then maker to maker. The TV show, Engine Masters tested different octanes on a dyno to see about performance and found almost No difference between 87 and 91 octanes. Check it out, its interesting for us gearheads.
I have a 2010 Silverado that has a dod/ vvt delete, mild cam, shorty headers and HP tuners tune. It is a flex fuel LMG gen 4 LS. Due to my tune I cant use E85. Id need some additional parts and sensors to run it. I also dont bother with 91 octane. Its a daily driver truck that runs 87 octane and keep it in Tow Haul mode most of the time. And Yes, sadly because I do haul a trailer often I had to write 2 tunes for this one truck.