So it will be tested in the woods prior to him actually NEEDING to use them...
You definitely want him to get used to them before he really needs them.
This anecdote has no bearing on all the marvelously adventurous dogs who accompany hikers on this forum, but it's kind of funny in retrospect: in 1994, we adopted a three-year-old retired racing greyhound, Dale. He was a splendid hound: big, tall, strong... only dog I ever saw with a well-developed set of buttocks. Not surprising, I suppose, he was a professional athlete and all that.
Well, Dale had a couple of significant weaknesses: he hated cold. He hated wind. And he really hated snow. Unfortunately for him, at the time, we lived on a small hillock overlooking Boston Harbor that was notably cold, windy, and some years, snowy. This resulted in innumberable agonizing late-night walks, dragging Dale mercilessly up and down the hill, trying to find a spot on the lee where he would finally drop his tail and dump. He would sooner have exploded than take a chance, if you know what I mean.
Anyway, back to your thread: my mom took pity on Dale and bought him a very fancy, very expensive set of booties to go with the heavy fleece track-coat he wore in cold weather. One cold, snowy morning, I bent down and carefully tied on all four booties and lead him outside. What ensued was high dog comedy, as he spent the next 10 minutes trying to violently shake all four feet -- simultaneously -- to get the booties off his feet, while I tried to get him to move forward toward the pooping grounds. If he could have levitated, he would have. Oh, and I never succeeded in getting the booties back on him again -- and he lived to the ripe old age of 15, the last several of which were in very snowy, very windy, very cold New Hampshire.
So yes, take the time to let your pup get used to the booties, preferably in a relaxed setting!