Put the liquid inside (basic acqueous layer + solvent) through the top opening of the separatory funnel using a normal funnel to help preventing spills. Wait for layers to separate, put a container under the "faucet"/stopcock opening, then open the stopcock so the lower layer is drained away. Once all the lower layer is drained, add some sodium carbonate water through the top opening, so that it picks up the rests of acqueous liquid that are around the walls, drain that again. Do maybe 3x washes. After washing, let it stand for some minutes so all the droplets of water fall down and drain them also. Then once you have just the solvent layer, drain it to a new container. Voilá
If you use a heavier-than-water solvent like DCM, it will be the bottom layer so its easier to work with (but DCM is not easy to find for some and you need to purify further because it also dissolves the impurities too well).
You cant work with STB, the plant matter would block the stopcock, you need to work with A/B. As for the amounts, depends on the size of your sep funnel. If you have a 1l separatory funnel, you can reduce your alkaloid solution to maybe 600ml, and have space for another 200ml or a bit more of solvent. Also depends how much mimosa (or cactus or whatever) you're playing around with in the first place. I suggest getting at least a 1L sep funnel, not less.