We recently graduated two homeschoolers who are now in college, and have a third with 5 years to go.
At the age of your children, I wouldn't know what curriculum to point you to, it's been a long time since we had kids that age, but honestly, at that level, basic reading, writing, arithmetic and some fun historical stories, crafts, etc. are all that's needed. If there are not ample amounts of fun mixed in, you're doing it wrong. Look into unit studies as well, our kids loved them at that age. When the older ones were junior high age we did a unit study on Lewis and Clark and traveled to various places on the Oregon Trail (mostly local for us). I had as much fun as they did.
I would suggest the most important thing you can do is to plant yourself in a community of other homeschool families and build relationships. You will likely find there are church programs, co-ops, etc, all of which are useful. My wife kind of went hog-wild and we probably now own more curriculums than three average homeschool families combined.
Classical Conversations is a nation-wide co-op that is used by many. Each of our kids did it for a year or two, but we decided in the end it wasn't the best fit for us. It is very regimented. I like the program a lot, but it's not as flexible as our kids needed.
The most important thing is to get plugged into the local homeschool community, though. And don't get intimidated, it's really easy to get intimidated. Trust that, regardless of what you mess up, your kids will still turn out well. If you look into how much they can learn in a few hours vs. an entire day in a traditional school environment, it will be an eye opener as to what's really required.
Probably the biggest benefit of homeschooling for us is that our kids never went through the "teenage rebellion" years. We have a great relationship with all three of our kids and never had to deal with that sort of thing. No drinking, drugs, fights, wild parties, etc.
Myself, coming from a broken family in which I was the rebellious one, I am continually amazed at how "grown up" my kids are, even the youngest one, because they are not immersed in the usual secular public school culture like I was at their age. It makes a huge difference in their character, and I've come to realize that getting into an Ivy League college is not the goal of their education.
Teaching them to love God and love learning is the goal. The rest will take care of itself in the end.
Just my 2 cents.