UMS aka USB Mass Storage is the way of accessing data most are familiar with, like SD cards and external hard drives. This option is not available on the S4. And the USB cable is not used for DLNA
To access your phone via PS3's DLNA:
** DLNA requires both devices to be on the same network.
1) Turn on DLNA/File Sharing under Settings -> Connections -> Nearby devices. Make sure there are no devices in the Not-allowed list.
2) Make sure Shared Contents has something checked for sharing.
3) On the PS3 make sure you turn on Media Server Connection under Network Settings
4) Go to Photo/Music/Video and click Search for Media Servers if your S4 does not appear immediately.
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If it ain't broke, use a sledge hammer.