The two primary problems with condoms are if they break or they slip off. Doubling up will give you a backup against breaking but probably will offer little help for slipping off since the surfaces between the two condoms will be high friction (latex to latex) and the surface between the inside one and the skin will be the same as with one condom. Maybe using two and putting a rubber band around the bottom end might help with the possibility of slipping off.
Increasing the thickness from the second one may also reduce the level of sensation, the primary objection most guys have to using them.
If your guy has one that fits, pays attention for slippage and doesn't do any acrobatics, that's about the best you can do with condoms. Good luck.
You might want to think about doubling-up on methods. Use the condom with a spermicide that is ok for use with latex condoms. Refresh the spermicide with each round. You also need to learn enough about your cycle to know when you're ovulating, and totally avoid having sex when it's possible for you to conceive. If this is going to be a regular thing, you might want to add a third method like oral contraception, injections, or whatever option you can your doctor decide is best for you.