First of all, you need to find a good curriculum to use with your child/children.  It helps if you know which learning style your child has and which teaching style you have! If they are a more hands on learner and enjoy making crafts and things with their hands, you might try Konos Character Curriculum.
If you and your child enjoy a work at your own pace approach, you might enjoy School of Tomorrow's ACE curriculum.
If you want to do a more traditional school setting, try Bob Jones University Press
or try ABEKA books.  These are both really great Christian/Home school text and workbook companies.
 Organization is another very important thing in homeschooling.  An organized home makes it much easier to concentrate on homeschooling and makes it much easier to find things that you need when you need them.  If you need some great hints on organizing, I recommend these books:
    Survival for Busy Women by Emilie Barnes
    The Messies Superguide by Sandra Felton
I also recommend that you get a good organizer book such as a Daytimer or Gregg and Sono Harris' Homeschool Family Organizer.
 A great avenue for both you and your kids to meet other homeschoolers and go together to field trips, play days, participate in athletic events, etc. is to join a good support group.  Visit my support groups page for links to Central Arkansas support groups and other support groups.
 I also recommend subscribing to a good homeschooling magazine.  It's really neat to hear how other parents across the nation do their homeschool and what has been successful for them. The mags also have lots of great new curriculum ads.  My personal favorites are Practical Homeschooling put out by Mary Pride's family
and The Teaching Home.