Start with Substance Power 200.

I don't think there is any financial advantage to buying them at the same time.

After you've enjoyed some substances (the legal kind), then you can decide if you'd like to delve into the world of creating and/or modifying your own substances.  Do you want to AUTHOR your own substances?  I got the "Indie Pack" which might not be offered any more, but is probably equivalent to Substance Live.

It's a lot of fun, both Substance Painter and Designer.  As mentioned, for now you need to adjust the output channels to be compatible with iClone, but sometime (per the "What to expect in 2016" thread) we will be able to use the "metallic/roughness" channels in iClone.

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iClone 7... Character Creator... Substance Designer/Painter... Blender... Audacity...
Desktop (homebuilt) - Windows 10, Ryzen 9 3900x CPU, GTX 1080 GPU (8GB), 32GB RAM, Asus X570 Pro motherboard, 2TB SSD, terabytes of disk space, dual  monitors.
Laptop - Windows 10, MSI GS63VR STEALTH-252, 16GB RAM, GTX 1060 (6GB), 256GB SSD and 1TB HDD

There's one other thing to consider in your purchase since Iclone announced the coming of PBR rendering. With Physically Based Rendering in the pipeline for 2016, then you're going to probably need to do some adjusting on the substance 200 if there's no update or anything covering it. When that happens, you're going to need something that can produce a PBR output, so you may be back to this quandary later on this year. Just keep that in the back of your mind.