Okay - I accidentally solved this. I kept trying to drag something in to label by but when I left it blank I was able to show labels and this time (I swear I tried that once) they showed up. A quick field fix of number format and voila percents. Hopefully I'll be able to recreate. Though I'm still not sure how that worked for the stacked bar. Thanks for the help anyway!
There are a couple of ways to get the totals to show up.
1. Place Measure Values on the label shelf.
2. Go to Analysis>Show Mark Labels
3. Click the drop down menu next to the Label Shelf and check the Show mark labels box.
Hope this answers your question!