Over all the years of home-schooling, one tries many options. It is only with the benefit of hindsight, that you can see the things that helped the most.

1. Organization. Homeschooling is less stressful when you are organized, by that I don't mean super-well, I just mean having some sort of routine. It is good to have a start time - ours was always 8am, when the children were fresh and alert. Some have a finishing time, but I always preferred to let the children finish when the work was finished, this provided them with the incentive to work and also avoided stopping them when they were in the middle of something complex or of great interest for them. It makes life easier for you and the rest of the family if you have particular times for things such as going to the library. Discipline is an important part of this, whilst not recommending physical punishment, it is important children understand the long-term and short-term, consequences of their behaviour (long-term may be not getting the career they want, short term may be some sort of withholding of 'treats' such as television viewing).
2. A place to do 'bookwork'. Whilst homeschooling is largely hands on, so learning matter is often covered in the kitchen cooking, outside gardening, on the sewing machine or computer, there are certain things which need to be done with and in books. Some people manage with the dining table, but this can become chaotic when you have a number of children and still use the dining table for other tasks! I always found it useful to have a 'school room' - one of the bedrooms with a large table and latterly a desk or two. More than anything it allowed my to consolidate things such as books, posters and craft items I used mainly for school.
3. The confidence. This will often be based on your own school experiences and your academic level. Don't feel that you can't do it because you didn't do well or get far in school, there are always ways around this if you have the urge and commitment to home-school. With the internet at your fingertips, you have access to some of the best teachers and classrooms in the world. There are often many people in the community who will help if you only ask.
4. A home-schooling support group. Join a homeschooling support group in your area, they are often great boosters of self-confidence as well as good socialization (there's that word!) for your children. If there is no support group - start one, often all it takes is a regular time and meeting place (2.30pm in a local park), then publicize this, maybe you have a local paper, certainly the librarian is a good person to inform as the word will most certainly get around.
5. The internet. As well as providing a wonderful learning environment, the internet can put you in touch with others who home-school, support groups and helpful organizations and publications. As always follow sensible rules for safe internet usage.
6. Good books. Whether you use a curriculum, pick textbooks your children work out of or workbooks for them to work in, you need to find ones that you can understand. The best for children are those which start at the beginning, and proceed step-by-step to the more advanced. Illustrations should be simple, and diagrams easy to follow. Be careful of 'busy' workbooks with lots of things on the page in no particular order. Also make sure there is enough work in them to be worth the money. Educational books are expensive and if they only ask the child to fill in one word here or there, ask yourself what the child gains by that, not forgetting you are paying! Always make sure you actually look through the books you plan to buy for your schooling.