Background on me: Web developer since 1994, PHP developer since 2000.
You can easily support hundreds of concurrent users (per minute, not per hour or daily) with a good PHP VPS setup. Don't think that you have to learn something new, just do it right from the start. People will tell you to build using this or that, but honestly PHP powers some of the biggest sites on the net, so ignore them. While there are limitations they can be easily overcome by a little planning, a good host, and some caching.
My setup has handled over 300 concurrent users with next to no slow down. I typically get sub 1.0 second page load times in Google Webmaster Tools, so it's a good template to start with. It can easily handle over 10,000 very active users a day (if you get more than that you can always scale up the hardware, I use a $50 per month VPS):
1. Start off with a good dedicated server or VPS. I use LiquidWeb or their cloud partner StormOnDemand. Excellent host with the best support that I've ever had in 17+ years as a developer. If in doubt call their 800 support number and count how many rings it takes to get a live person. Storm plans start at $35 a month and you can scale up to beastly 96GB servers quickly.
2. Install APC (or another opcode cache). the guys at LiquidWeb/Storm should be able to do this for you. You can make pages load 10x faster with this.
3. Use a good FAST framework. I love CodeIginter as it's simple, but you can do awesome things with it. It also has full page caching that is nearly as fast as plain HTML. You can deliver thousands of pages per minute if you set things up properly.
4. Put assets (images, css, etc.) in to a folder with a "far future expires" .htaccess and properly version them. This will mean that your visitors will download it (and request it) one time. Follow Yahoo and Google's general guidelines on high performance web sites and you'll do fine (Good Performance == Good SEO).
5. Plan ahead. Make sure you set things up so that you can move to dedicated database servers (easy with CodeIgniter) and cache as much as possible with APC (or whatever opcode cache you use).
If any of this sounds like a lot it's most of the same stuff you would do with any other language. The second and third biggest problems most pages have are poor shared hosts and not properly caching. Once you get those two issues taken care of the rest is cake. The number one problem is getting the page made in the first place. That's why I would say to use what you know, and get it done. Even if you screw up you can always go back and fix it later. Better to get something out there ASAP. Trial by fire teaches you a lot.
Feel free to contact me for help.