As a parent that pulled her kids out of public school to homeschool them I understand your fears. My kids were in 1st grade and Kindergarten when we pulled them out. They now are 3rd and 2nd grade. We just started our second year of homeschooling.
My advice is really no different then what others have already posted.
1) Make sure you know YOUR state laws.
HSLDA: State Laws is a good resource for that.
2) Have your goals and price in mind prior to looking for material-curriculum. Homeschooling can be done for little to no cost or it would cost $1,000s of dollars per child. So have an idea of what your willing to spend and what you want prior to looking at curriculum. Chances are you’ll be able to find something that fits your needs within your budget. You just have to have a general idea of what those are prior to shopping.
As for actual curriculum resources there are a few choices. Seeing this is a Catholic-Board I can assume you would want Catholic Resources, but instead of limiting you to just that, I’ll direct to my blog where I have
several resources listed; Catholic and Non-Catholic Resources. The list on my site is NOT complete, there are a lot more resources out there, but perhaps it would be a good starting point.
And lastly, don’t be afraid of change. You’ll know in a short time if a curriculum, lesson plans, or scheduling is working for your family. The first year you can get a lot done, but it is also an year of figuring out what will work and what will not work. Honestly even though this is our second year, I’m still learning what works or does not work.

I have a better handle on it now then I did this time last year.