I'm having this problem with the third sprocket.. it reaches nicely over 1 and 2, but is slightly too the inside of the third sprocket so think it may need an LBS in time. I am thinking I can function on 12 gears rather than 18 for a while as I'm a novice.
Sounds to me like your limit screws are set incorrectly. It's really quite easy to adjust!
If you look on the front dérailleur (the mechanism that actually pushes the chain on to the next gear) there should be two small phillips/cross head screws, one should have a small "H" written next to it, the other a small "L", which stand for high and low limit.
These screws stop the dérailleur going too far and pushing the chain off the end of the cogs, but if they are adjusted incorrectly they can also stop you getting in to the gears at the more extreme end of the ratios. In this case your largest gear on the chainset.
If you unscrew the screw marked with a "H" this should allow the dérailleur to move slightly further out, and hopefully get in to the biggest gear (assuming the cable has been fitted correctly). Do small adjustments at a time, half turns of the adjustment screw are good, then go for a small test ride up the street.
If the chain comes right off the end then you've unscrewed it too far.