I buy all workbooks etc from big bookshops where they are arranged in key stage sections. I find that works well. Also, I take a sneeky peek at school websites - they usually have their curriculum plans for each year on them. I find that useful for nicking topic ideas for things like geography and history.
My ds is almost 7, and w first started HE when he was 5 (half way through reception). He was so easily distracted at first, didn't want to do anything, but it got a lot easier once he could read, he got more confident and started to enjoy the work we were doing.
I started him on education city.com as well, he loved being able to do the learning games on the PC himself, and I found that really helped with concentration. They are quite short activiies, especially for reception and most kids I know who use them really enjoy it.
We also did really short bursts of work at first, 10 - 20 mins a few times a day and then let him run round and play for an hour or two inbetween. He couldn't read/recognise letters at all when he left school, so we had to begin with basic phonics, so it was better to do it in short spurts.
We used Oxford Reading tree, I bought the books in big packs from amazon. You can get work books to go along with some of the levels too. Not everyone is a fan of ORT, but it gave me piece of mind to know exactly where ds was with his reading compared to kids of his age in school. Although, if you go down that route, she will end up at a much higher level of the books than school age kids, just because she will be getting one on one reading everyday and can go through books/levels at her own pace rather than when a teacher deems it so! We only used ORT for reception and part of year one, as he tore through the reading levels and moved on to reading any book he liked (this was within 6 months for a child who could not read his own name at 5 and a half when he was taken out of school!). They really helped him.
Don't know what to say about your neighbors though. Can you tell them you intend to teach inbetween certain times, or would that be terribly rude? I suppose it depends on how good friends you are. It would drive me up the wall too.