より contrasts a quality of two things. The thing that comes immediately before より has less of that quality than the other thing in the sentence. The most basic structure is AよりB, but B can come at other places in the sentence.
Here are some examples:
勉強より実習の方が役に立つ - Hands-on experience (実習) is more useful (quality) than studying (勉強). AよりB
水は食べ物より大切 - Water is more important (quality) than food. BはAより
に合わせて is more simply structured. It always follows the Aに合わせて・に合わせたB structure. B is befitting A. に合わせて modifies verbs, while に合わせた modifies nouns.
Here are some examples:
生徒の年齢に合わせて活動を変える必要がある - It is necessary to change your activities to fit the age of your students. Here it is the action - changing the activities - that is being talked about, so you use に合わせて.
生徒の年齢に合わせた活動を準備した - I prepared activities befitting my students’ ages. Here, you’re talking about the activities themselves, so you use に合わせた.
Hope that helps! As always, there may be holes in my knowledge/my understanding may not be complete, so if anyone has any corrections then by all means correct me haha