The S5 doesn't have Fastboot mode. You have to use Download Mode and Odin.
Fastboot is a Google tool you'll find on Nexus and other devices, it's much easier to use.
I think you can 'sideload with ADB' in the stock Recovery Mode. Press Vol Up + Power + Home to get there. I'm not sure how much of ADB you can use from there. Most install TWRP or a custom recovery to be able to install .zip based ROMs like CyanogenMod or CF-auto-root.
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