There are some good answers here already. As a developer who has worked as a 'one-man-band' company for a number of years, occasionally bringing in sub contracts (and briefly, some employees), but mostly working alone, I have a few points for you to consider that I don't think were covered in the other answers.
1) Working at home is much, much harder than most people appreciate. I had a terrible time working from home to begin with, then I got a little 'lock-up' office and things changed dramatically. Recently I've had to go back to working at home and it can very difficult to deal with the distractions (and right on-cue as I type this, the cat walks in and meows at me for attention!)
If you can get yourself a room 'away/apart' from the rest of the house, it will help. If you can get a room where you can close the door, and the room has no other real purpose than to be your office, so much the better. You really want to try and maintain this idea of you being at work, both in your head and in the heads of the other people in the house. While you're working, you're not really able to run out for groceries or do other domestic chores, however much they may play on your mind etc. Save them up for your lunch break, exactly as you would do at work. Even little 'psychological' things, like putting your shoes on before you go work, can help make the distinction in your head.
2) The biggest risk when you work alone on projects that are not subject to peer review with other developers is not the potential to write bad code. Instead, it's about overlooking functionality and not getting the requirements right. And, to a lesser but still important degree, that you don't disappear 'up your own arse' with things like user interface or 'clever' features that don't actually add any bottom line value.
As long as the testing proves that your code works, the real cost of bad code (or rather, code that another developer would help you improve) on an 'internal' project is minimal, especially if this is a 'start-up' project and you're just trying to get something out there for her to use.
But if some key component of the system is overlooked, or your understanding of it is flawed, the whole enterprise is thrown into jeopardy. I'd say you need to quickly get a non-functional mock-up/prototype so that your wife can role-play with it and take some 'ownership' of elements like work-flow and overall functionality.
No-one else is likely to see your code, in all honesty, and so as long as it does what it's supposed to do, I'd not be too concerned about HOW it does it - I'd be more worried about WHAT it does and WHY, and those are things that your 'customer' can help you with.
3) Try to work on small, closely defined pieces one at a time. When you're on your own it can be hard to stay motivated if you don't feel like you're making a lot of progress. You need to plan your work so that there is some degree of visible progress each week, however arbitrary or 'fake' it really is. Once I've mocked up enough of my screens and controls for role play, I pick one to start 'fleshing out' and I try not to get dragged into the other parts of the program that it will ultimately interact with. Leaving functions and procedure calls as empty stubs helps. You go back over time and fill them in, but you don't ever want to be in a situation where you've spent a whole week typing code into the same 2 or 3 unit files and don't have anything tangible to show for it - those kind of things can sap your momentum if you don't keep an eye on them.
I've got more but I don't know how useful you're finding this and it's probably too wordy already so I'll stop there (for now?)
Whatever you do, best of luck with it!