Just to be clear what do you want to do with the raspberry pi and plex?
Are we talking about using the Pi as a plex client to watch movies or using a Pi to provide a plex media service to other clients?
Because the Pi will work really well as a Plex client to watch media.
It won't be a very effective Plex server if you need transcoding. If you don't know what Plex transcoding is; it is the on the fly translation of a media format the client does not support into a format it does support. Transcoding video files is very CPU intensive and the general consensus is the Pi sucks at video transcoding.
If the vast majority of the media files are already in a compatible format with your Plex clients, then you don't have to worry about it. If a large portion or most frequently used part of your library needs to be transcoded, then you will need better hardware than a Pi for a Plex server or you are going to get issues with playback.
Also a potential issue is number of clients. A Pi2 running Plex server can probably handle 1 or 2 clients at a time and then get pretty finicky if you add more than that.
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