I suggest that the chromecast android app can connect the chromest to an existing DLNA server, insted of the PMS, if the user chooses to, and the media is compatible with chromecast (mp4, level41, etc).
The ideia is that *IF* the same video is available from two differents sources, for exemple, in the case of a NAS, where the user maps a SMB network share to the computer running PMS, and PMS performs the library scan and metadata extraction, and also the NAS has an embebded DLNA server, that shares the same files, but over the DLNA protocol.
The library can associate multiple sources for the same file, for exemple: and <http://nas_ip_address/myvideo>, and if the PMS is not available (ex: pms computer turned off), the chromecast app can stream directly from the NAS to chromecast.
This kind of streaming was already available in Android apps like BubbleUPnP, and 'Playto Chromecast'. But the PMS library, with its metadata, is far superior to the others apps. It will be a 'plexpass' superb feature that you can stream the videos from your NAS, without need to turn on the computer to run PMS, but with the incredible visual and metadata.