Not something men are in general very good at. General advice here is to actually do skin care. Basic requirements for half-decent skin: always use moisturizer (every day), especially after shaving; use body lotion - again, especially after shaving; always remove your make-up thoroughly before going to bed (any oil-based cream is good at this; dedicated eye-makeup remover can be a good idea); consider using something other than bog-standard soap for routine washing - use a decnt moisturized soap (widely available) and perhaps use a facial scrub (and/or a face mask every now and then). While not all women are totally scrupulous about this, men usually have farther to go ... You do not need to go quite as far as the classic Cosmo. routine of cleanse, tone, moisturize, but something more than a quick wipe with a flannel does help!
This is not a "how to shave" gude, but just a couple of hints for the specific purpose of crossdressing. The aim is obviously to get as smooth a shave as possible, and to reduce the amount of shadow left, or liable to develop. Two key tips have come my way. Firstly make sure you shave in both directions - "with the grain" and then "against the grain." Secondly, the application of baby oil before shaving makes for a smoother shave, and also, according to some, makes the makeup go on more easily. Splash the face with cold water after shaving in order to close the pores. As for type of razor, we all have our favourites, but the "Sensor Excel" from Gillette is definitely worth considering if you haven't tried it. Excess shadow (or shaving rash, or rough skin) can be tackled by the use of camouflage cream, such as Dermacolor.
For the serious-minded and those with a decent (or, indeed, any) income, there is the option of electrolysis. As well as cost, there is the issue for some of pain. You can get the treatment from most beauty clinics, so if you have the nerve and the money, go for it. If TS, you can get this through the NHS, I believe.
Therre are a number of options here - shaving, depilatory cream, the epilady (! - electric hair extracter) waxing and electrolysis. For the latter, see above, but note that even more hair is involved here, so it is perhaps only really worth considering for the chest (or arms if they are a real problem). Other methods are regularly used by women on their legs, and are plentyt good ebnough for us, despite our usually hairier lot.
Firstly, waxing: I hear mixed reports of self-waxing products, and a professional job may be better (consult TV Guide for places, or nip down to your local beauty clinic). If you're game for the all-over body-wax, then go for it, but I warn you ... . Women assure me that men are the fundamentally weaker sex, because they generally can't take a leg-waxing.
If you go for wax, shave first and then let the hair grow a little (third of an inch). The same holds if you want to use an "epilady" or similar product. Opinion is divided on the pain of such a device. If you have a high pain threshold, then this could be for you - the effects do last longer than shaving.
Depilatory cream may also be for you. Try it. It doesn't work for me, but SW assures me it does for her. Perhaps use it slightly more liberally than recommended, or certainly near the upper limits.
But for all-round effectiveness and general applicability, you can't beat shaving. Ideal for arms and legs, but may cause a rash at first on chest. If you're shaving from scratch, use an electric razor with beard-trimmer to get the hair-length down and avoid clogging up the razor. Use a woman's razor, with a moisturising strip. Also use shaving soap, to avoid a rash, and for a closer, smoother shave. You can also try the application of baby oil before getting the blade out. Especially if you are shaving for the first time, make sure it is a new razor. I use "Gillette Sensor for Women" which does work very well. (If you're desperate, you can always re-use a facial razor at a pinch.) Whatever you do, use body lotion after you've shaved.
There are ways to avoid having to shave, but if you have never tried all-over hair-removal, I would urge you to try the experience. Hair can totally ruin the feel of the clothes, and hair with tights has to be one of the world's great abominations. Oh, and your partner may even prefer you hairless!