Instead of focusing on the "first day of school" new outfit, let your elementary school child choose and hang up the whole week's worth of outfits for the first week of school. Each outfit does not need to be new; just the planning and anticipation of wearing each favorite item of clothing gives something exciting to look forward to each day as the child wakes.
On the first day of school, everything is so new and different, your children likely have many things to report. Don't let the excitement die on the second day. At the dinner table or while having their after-school snack, ask the kids to give a second-day summary of their teacher and classroom. Ask what their teacher's personality is like. List on a paper what they think they will need to do to be successful in the class, and ask what they think they are going to like the most. Have them tell you one high point of the day. You can continue the daily high point past the second day of school.
Older children often have less excitement about the first day of school, and you may find it harder to get them to share things with you about school. Additionally, middle and high school students rarely have a supply list before the school begins, unlike elementary school students. To make the second day of school special for them, plan a trip to the store to pick up their needed supplies. As you are shopping, you may be able to start conversations about particular teachers or what they like about certain classes. You can make it a second day of the school year tradition, and give the older children something to anticipate.
Although you'll want to feed your child breakfast every day before school, make the second day of school special. Get everyone up early and take them out for a "feels like the weekend" breakfast at a pancake house or other favorite restaurant on the second day of school. Again, it gives them something to look forward to and keeps the excitement of the new school year fresh.