The only way to Guarantee that specifc tapes will be used by specific jobs is to parition the library (i assume that you are using a library) Think if the partitions as virtual tapoeo drives.
From the devices tab, right click the library\Create Partition. Then change/create your jobs to point to a specific partition. Partiutions can be more than one slot, and you can still point jobs to the library as a whole if yo uwihs
You can come close to using specific tapes with proper media management, but cannot guarantee it.
As to why the second tape is not from the correct media set, do you have "Use Overwritable Tapes in Target Media Set before Scratch Tapes" selected (Tools\Options\Media Management I think)
If this is not selected, Backup Exec will us the "oldest" tape that it can see, regardless of what media set it belongs to. Oldest meaning in scratch status longest.