I've used Mold-Max and OOMOO. I checked the product specs at the Smooth-On site for the XLS. It is for "hot" resins which are large and intricate. Stay away from the platinum-cure urethane rubbers (pricy and not as suitable for modeling applications).
The 10 to 40 indicate the Shore Hardness of the finished rubber. The lower the number the more jelly-like. The higher the number the more firm. 40 and above may be too stiff to easily remove the master on a one-piece mold resulting in tear-out. But 40 may be good for a two-piee mold.
Mold-max and XLS are 100:10 (10:1) mixes. They are a little more work to get the proportions right -- you need a scale or good measuring cups. Not as forgiving if you dont have the tools. Vacuum degassing is recommended for XLS and MoldMax
OOMOO is a 1:1 mix by volume. It can also take a bit of too much of one or the other in the ratio, by as much as 10% I've been told. More forgiving. I use 1 ounce condiment cups from the restaurant supply store. Measure, pour, scrape and discard. I mix in a plastic cup. Mix, pour scrape, and discard. Degassing is not necessary (be careful to limit entraining bubbles when mixing).
I switched from Mold-Max to OOMOO because of the 1:1 mix and degassing. I found that I had better results on my molds getting the ratios right. I've used both OOMOO-25 and OOMOO-30. Even though the demold time is longer for the -30, the molds using -25 were not as robust. My preference is -30
I don't have a vacuum pump, so I pressurize both the rubber and the resin. The molds seem to give better results when pressurized than when not. But as pointed out, pressure is not required if your mold is well thought out with minimal undercuts.
Check the distributor list at the Smooth-On site, or call the Smooth-On help line. Tell the hlep line or rep at the disrtibutor what you want to do and ask for product recommendations. There is a distributor just over in Dallas from where I am and they've been helpful answering questions. Get on their mailing list. Smooth-On runs some local seminars which allow you a hands-on opportunity to try their products. Also having a distributor handy allows you to make an over the counter purchase when you need the stuff now - not wait on shipping.