Is Arduino FIO a good choice for each of these units? And I could use a XBee explorer USB on my computer to communicate with them.
Maybe. The hardest part of the project is going to be getting all the XBees configured to talk to each other. The FIO is really intended to be one point in a point-to-point (i.e. two node) network, not as one point in a mesh network. However, that really matters only if you plan to remotely program the FIO.
I am lacking in experience here
Well, this isn't going to help any.