First, don't bother hauling an iMac to an Apple Store. Apple Geniuses will not upgrade devices, only replace parts "in kind." If you now have 8GB now, they will only remove it and replace it with 8GB. No more. And that model does NOT have user-serviceable RAM. You have to cut into a sealed case and gut the computer to get to the RAM slots.
That leaves the Apple Authorized Service Provider and, per the Apple article on RAM upgrades, not all Apple Authorized Service Providers will do that work. Call ahead to verify they will even consider doing it. It is slow, delicate work and ones I've talked with say they have to charge two hours of labor at US$60-80/hour. That's before the cost of the RAM and the reseal kit. Some choose not to do such upgrades because they must charge the customer too much for too little gain.
Second, at the time of the test, your iMac was NOT starved for RAM. The new metrics, well "new" since 2013, are Pressure and Swap used. The indicator in the posted report that says RAM is not the issue is Swap Used which is zero in your case. You can use Activity Monitor to see the Memory Pressure. The 2013 memory management changes made macOS work much better with smaller amounts of RAM, so Memory Used is not longer a key metric.
Adding RAM almost never speeds up a Mac, in spite of what all the RAM vendors proclaim, and slow boots are NOT a RAM issue.
Third, Your Fusion drive is performing well, and at speeds appropriate to that iMac model based on other EtreCheck drive scores I've collected:
Write speed: 884 MB/s
Read speed: 1471 MB/s
In fact, your important Writes are faster than expected. Usually in 21.5-inch iMacs with Fusion drives, Writes are 600-800MB/sec.
...and am thinking of buying an external SSD to use as the startup disk ...
An external USB 3 SATA 6G SSD can do writes/reads no faster than 400MB/sec, meaning that would be a step in the wrong direction and a waste of money. The only external that would be faster than your current drive is a Thunderbolt 3 or 4 external, and they are not cheap, but stinkin' fast:
https://eshop.macsales.com/shop/owc-envoy-pro-fx
Fourth, you have remnants of CleanMyMac that must go. I've seen scores of Etrecheck report here where removing CMM improved drive scores by up to 40%. "Cleaning" apps WILL slow your computer because they interfere with elegant, automated self-maintenance routines you paid Apple to build into the OS. That alone could be the source of your slow boot times.
Catlike, Macs clean themselves with no outside help. Their even self-defrag their drives.