Funny that those options are totally separate from the normal right-hand list of settings. No wonder I couldn't find it.
yes, you are not the only one who didn't find this.
Today, I saw a Cura 2.6 demo where the visibility of this option is improved.
Layer view is your friend. You can see the part in layer view. In the top right region you can click on the left or right extruder and the layer view highlights in brighter colors what will print in that material.
As a hack, if you can't get the slicer to do it, you can slice for pla but print with pva but alter the temperature (first find out default print temp for pla and pva then put the offset into the tune menu when it starts printing).
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