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OK, unless you have some defaults changed, it should go like this...
1. New file, whatever size/specs.
2. New layer.
3. Draw shape.
4. Edit blending options on this shape if needed.
5. Create another new layer.
6. Draw next shape.
7. Repeat step 4.
If you are working on different layers, and the layers are not linked, the blending options should only apply to the currently selected layer.
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