It works great but you won't escape the merriad of system folders in Documents or Pictures that way. Apps, games and the OS itself flooding these folders is the main problem why file management on Windows sucks.
Historically /bin and /sbin contained the binaries that were necessary to bring up the system (especially to mount the /usr partition, which was "best practice" to have separately from the root and /boot partitions). Nowadays most distros just symlink them to /usr/(s)bin
/usr/sbin is for utilites that only root should use, whereas /usr/bin is for regular applications managed by your system (i.e.: your distro's default package manager).