You'll need to record the voice lines with the same filenames as the sounds they're replacing, then pack the new sound/vo folder into a new VPK and rebuild the audio cache. Unfortunately you won't be able to hear them in the game until you do this, so it'll probably be easiest to record all the sound first, then do the packing. (It used to be a lot easier to do this, but Steampipe broke the other method.)
Just putting files into portal/sound/vo directly, since things outside a GCF had higher priority than things inside one.