It's not very complicated but a little tricky in places. First of all you need the md5 IO script for Blender... I believe the one I'm using is this:
Setup: You must have one or more mesh objects rigged to an armature as usual. Each mesh object represents a different material, the name of the material on each object represents the texture that material will point to. Additionally every surface on the mesh must be UV unwrapped, whereas the bones must be on the armature layer where the script expects it (layer 5 by default I think).
For the md5mesh: Just select both the mesh and the rig, and export to md5mesh. Disable reorient as this seems to mess up the rotation.
For the md5anim: On the control armature, select the armature action of the animation you wish to export. Make sure to set the start frame of the scene to 1 and the end frame to the last frame of that animation! Then once again select both the mesh and rig, and export to md5anim. Again disable reorient as this seems to rotate it on its own.
If you want an example setup, the ready blend sources of the bow and Xonotic characters are both included in the repository. You can find them here:
Very cool. Will study these. If I get that far, I shall ask for more info on the defs and how to setup the weapons and stuff like that! Thanks for taking the time.